(DE85005809)
IDS
Norman John J.
J.
Date Published
October 1986
Under Contract No. ACl
For U.S. llenartmenl of l:il
Office Bartlesville, Oklahoma
By Recon Three !:!ridges.
Inc.
and Yates and Auberle Oak Illinois
0777
PREFACE This study was undertaken for the u.s. Department of Energy to identify waste liquid hydrocarbon streams possibly susceptible to recovery and reuse, and to suggest research and development programs to accomplish this purpose. The work was initiated on July 12, 1983 under U.S. Department of Energy Contract No. DEAC19-83BC10777. The methodology used to accomplish the required objectives included an in-depth examination of the literature; contacts with the U.S. Environmental Protection Agency, waste exchanges, and trade association; and analysis of the data obtained to detect worthwhile research and development opportunities. This report completes the required tasks.
i
ABSTRACT Liquid hydrocarbons are critical to the u.s. economy. Yet large quantities are wasted, with a very negative impact on our environment. This study has identified waste hydrocarbon liquids equivalent to about one percent of our petroleum consumption, with a potential fuel value of over two billion dollars per year. At least an equal amount is believed to be emitted to the air. waste hydrocarbons are usually found in complex mixtures, aqueous solutions, emulsions, and suspensions, and in air emissions, thus difficult to recover and reuse. Recovery and reuse are possible, using modifications of known technology, but implementation of these modifications requires research and development in areas suggested in this report.
ii
TABLE OF CONTENTS Page
SUMMARY
1
INTRODUCTION
3
IDENTIFICATION OF WASTE HYDROCARBON LIQUIDS Litera ture Search Waste Exchan ges u.s. EPA Region al Office s u.s. EPA Office of Solid Waste Trade Associ ations Waste Hydroc arbon Invent ory ALTERNATIVE USES
6 7 7 9 9
10 13 15
Reduce d Genera tion Reuse Fuels Chemi cal/Pet rochem ical/Ot her Raw Materi als Constr uction Indust ry FEASIBLE PROCESS
16 17 18 19 21
22
Re-Ref ining and Reproc essing Indust ry Virgin Petrole um Refinin g Indust ry Chemic al/Petr oleum Indust ry In-Pla nt Recycl ing Proces ses Recove ry from Wastew ater Recove ry from Air Emissi ons Other Feasib le Proces ses RESEARCH AND DEVELOPMENT POSSIB ILITIES ·combu stion Proces s and Produc t Modifi cations Recove ry from Aqueou s Solutio ns Recove ry from Aqueou s Emulsi ons and suspen sions Recove ry from Gaseou s Emissi ons Prepar ation of Chemic al and Fuel Raw Materi als Integr ated Recycl ing Facili ties Other R&D Possib ilities CURRENT STATUS OF EACH OF THE TWENTY-THREE (23) MOST SIGNIFICANT WASTE HYDROCARBON STREAMS Purpos e Method s Result s summar y
22 24
25 26
27 28 29 30 30 30 31
32 32 32 33 35
36 36 36 36 43
iii
REFERENCES
48
APPENDICES A. WASTE DATA COMPILATION B. WASTE EXCHANGES C. INFORMATION FROM U.S. ENVIRONMENTAL PROTECTION AGENCY D. KEY WORDS FOR COMPUTERIZED SEARCH
iv
LIST OF TABLES Page Table 1. Coal Tar Chemicals 1976 Data
12
Table 2. Most Significant Waste Streams
14
Figure 1. Waste "Hydrocarbon" Recycle Refinery
34
v
SUMMARY Their importance as the prime source of energy for transportation and as a chemical raw material establishes liquid hydrocarbons near the top of the list of commodities critical to the U.S. economy. Yet large quantities are wasted, with a very negative impact on our environment. This study has identified waste hydrocarbon liquids with a total heating value of at least 0.4 quads. This is only about one percent of our petroleum consumption, but with a potential fuel value of over two billion dollars per year. At least an equal amount is believed to be emitted to the air. Waste hydrocarbons are usually found in complex mixtures, aqueous solutions, emulsions, and suspensions, and in air emissions, thus difficult to recovery and reuse. recovery and reuse are possible, using modifications of known technology, but implementation of these modifications requires research and development in areas suggested in this report. Among the research and development suggestions made, following are considered to hold the most promise:
the
1.
Development of methods and materials useful for heat recovery when burning waste hydrocarbons containing halides and other precursors of corrosive combustion products.
2.
Development of replacements for solvent coating systems which do not require liquid solvents, e.g. aqueous, electrostatic, and fluidized-bed coating systems; or systems which simply decrease the amount of solvents required.
3.
Development of improved methods for recovering waste hydrocarbon from aqueous solutions, including azeotropic distillation, stripping, extraction, adsorption, and membrane processes.
4.
Development of improved methods for recovering waste hydrocarbons from aqueous emulsions and suspensions.
5.
Development of improved methods for recovering waste hydrocarbons from gaseous emissions, including adsorption and high boiling liquid absorption.
6.
Development of methods for preparing raw materials such as crude fuels, olefins, and hydrogen/carbon monoxide mixtures from waste hydrocarbons by modified petroleum refining and chemical processes. -1-
7.
Develo pment of a techni cally and econom ically feasib le flow sheet to recycl e virtua lly any waste hydroc arbon stream in an enviro nmenta lly sound manner .
8.
An in-dep th analys is of U.S. EPA hazard ous waste survey data which are just now becomi ng availa ble. This would requir e an agreem ent betwee n DOE and EPA.
9.
A survey of waste hydroc arbons arising from produc tion of crude petrole um, includ ing new wells, second ary and tertia ry recove ry, and existin g waste oil lagoon s. It is believe d that this source of waste hydroc arbons is very large, but no data on the subjec t are known to exist.
10.
Defini tion of parame ters which would allow some waste hydroc arbons to be used in roofing and road asphal ts.
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INTRODUCTION During this century liquid hydroca rbons have become the predomi nant source of energy for transpo rtation, a vital source for other forms of energy, the feedsto ck of choice for most chemica l and plastics process es, and the primary source of wax and lubrica nts. In spite of the current glut of petroleu m and natural gas, there has arisen a widespre ad understa nding that finite supplies warrant maximum efforts toward conserv ation. even 1 imi ted success in conserv ation can reap large rewards in limitin g depend ence on uncont rollable foreign sources , in reducin g trade deficit s, and in direct dollar rewards . For example , conserv ation of only 0.1% to 0.2% of the 13-18 million s of barrels per day of liquid hydroca rbons used in the u.s. could easily be worth $200-40 0,000,0 00 per year dependi ng on the hydroca rbon type. Many solvents and other finished hydroca rbons are valued in excess of $2. per gallon while fuels are present ly valued at around $1. per gallon. The incentiv e to conserve hydroca rbons is clear. However , since most of the hydrocar bon conserv ation research during the past 1015 years has been directed toward used lubrica ting oils, there is a gap in the informa tion concern ing other waste hydroca rbons which previou s studies have shown to be as prevale nt, or possibly even more prevale nt that used lubrica ting oils (1, 2). This study has been designed to: quantit ies, proper ties, and current docume nt the recover y practice s for waste hydroca rbon liquids that might be availab le for some sort of energy and resource recover y, includi ng those from sources other than petroleu m and natural gas liquids. show the role that current recycli ng and petroleu m refinin g technol ogy can play in waste hydroca rbon recovery . provid e a detaile d discuss ion of researc h and develop ment which could improve waste hydroca rbon recovery .
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The follow ing defin itions have been formu lated for purpo ses of this study : Waste Hydro carbo n - Hydro carbon s and relate d organ ic mater whose prope rties and contam inants , includ ing water , may interfials with use as fuels , or as norma l comm ercial produ cts, or ere as feedst ocks for proce sses design ed to prepa re such produ cts. These hydro carbon s and relate d organ ic mater ials includ e liquid s, gases which are relati vely easy to liquef y (propa ne or heavi er) , and solid s and semi- liquid s which can be lique fied by heatin g witho ut signi fican t crack ing (usua lly 600°F or less) . Chem ically , the waste hydro carbon s may range from hydro carbon s compo sed prima rily of carbo n and hydro gen atoms to organ ic mate rials which may conta in subst antial amoun ts of eleme nts such as oxyge n, sulfu r, nitrog en, halid es, variou s metal s, and other s. Used oils, waste oils, and used solve nts are includ ed. Used Oil - Inclu des all used petrol eum produ cts (inclu ding lubri cants , hydra ulic fluid s, prese rvativ es, metal worki ng fluid s, waxes , and insula ting fluids ), as well as contam inated fuels, whose chara cteris tics have change d since being origin manu factur ed, but which may be suita ble for its origi nalally or simil ar uses throug h an effec tive recyc ling proce ss. Waste Oil Inclu des all used petro leum produ cts whose chara cteris tics have change d so marke dly since being origin ally manu factur ed that they have becom e techn ically or econo micall y unsui table for recyc ling to their origin al use. Used Solve nts - Includ es all used organ ic fluids contam inated a resul t of use for solve nt, clean ing, thinn ing, and similas ar purpo ses. Used solve nts are usual ly volat ile in natur e. They inclu de hydro carbo ns, halog enate d hydro carbo ns, oxyge nated hydro carbon s, and mixtu res or other simil ar types of mater ials. Recyc ling - The gener ic term for using or proce ssing waste hydro carbo ns to recov ery usefu l energy or mater ials. Includ es blend ing, re-re finin g, repro cessi ng, reclai ming , and other proce sses to prepa re usefu l produ cts. Re-re fining - The proce ss of recyc ling used oil to produ lubric ating oil base stock . Re-re fining may includ e distil latio ce hydro treati ng andjo r treatm ents emplo ying acid, caust ic, solve n, nt, clay and/o r other chemi cals.
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Reclaim ing - The use of separa tion method s to remove contam inants from waste hydroc arbons , or conver sely to recove r hydroc arbons from waste stream s such as aqueou s emulsi ons and suspen sions. The metho ds used may includ e settli ng, heatin g, dehyd ration , filtrat ion, centrif uging, distill ation, adsorp tion, and others . Reproc essing - Refers to the reclaim ing of used oil or waste oil primar ily to prepar e fuels andjor fuel blendin g stocks . Blendi ng - The proces s of mixing waste hydroc arbons or recycle d produc ts with virgin petrole um produc ts so as to prepar e a fuel which meets specif ication s for the intende d use. It should be noted that the use of the term hydroc arbons in this report genera lly refers both to hydroc arbon and other organi c · liquid s.
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IDENTIFICATION OF WASTE HYDROCARBON LIQUIDS Waste hydro carbo ns usual ly arise situat ions:
from one of the follow ing
uncon verted react ants or interm ediate compo unds in chemi cal proce sses (poor yield) bypro ducts produ ced in a chemi cal proce ss becau se of comp eting paral lel or conse cutiv e react ions (poor selec tivity ) norma l bypro ducts produ ced in some chemi cal proce sses solve nts, heat carri ers, catal ysts and other nonreacta nts someti mes used in chemi cal proce sses raw mater ial compo nents discar ded during recov ery of usefu l produ cts clean ing of equipm ent used for variou s purpo ses spills of organ ic mater ials off-s pecif icatio n raw mate rials, produ cts (inclu ding fuels)
interm ediate s, and
contam inatio n during the use of hydro carbon s and other organ ic liquid s for lubric ating , hydra ulic, solve nt and simil ar purpo ses Very often waste hydro carbo ns are found in aqueo us soluti ons, emuls ions, and suspe nsions --som etime s from an interm ediate step in waste water treatm ent proce sses or from air emiss ion purif icatio n, e.g. water scrub bing or adsor ption with steam stripp ing. Air emiss ion purif icatio n proce sses can also resul t in nonaq ueous waste hydro carbon s, e.g. by conde nsatio n. The broad varie ty of waste hydro carbo ns and the diver sity of their sourc es make the task of identi fying and quant ifying them very form idabl e. In an attem pt to devel op a comp rehen sive inven tory of waste hydro carbon liquid s, sever al metho ds of resear ch were under taken. Litera ture search es were perfor med data and abstr acts review ed to selec t articl es and repor ts cover ing waste hydro carbo ns. Interv iews were condu cted with all region al u.s. EPA offic es. The u.s. EPA Offic e of Solid Waste in Washi ngton, D.C. provi ded infor matio n on some hydro carbo ns that consid ered hazard ous. Interv iews were condu cted with all of are princ ipal waste excha nges in the u.s., and variou s repor ts the and perio dic publi catio ns were obtain ed. Each of these appro aches towar d inven tory develo pment is discus sed below , follow ed by a discu ssion of the resul ting inven tory of waste hydro carbo ns. -6-
Literature Search Citations from Engineering Index, NTIS, and other data bases from previous literature searches were reviewed for relevant articles and reports (3, 4, 5, 6). Key works presented in Appendix D were used for additional searches including Chemical Abstracts. Surprisingly, very little useful information came from these searches. Very few abstracts revealed information on waste hydrocarbon liquids. Most articles and reports address virgin hydrocarbon processing or hydro·carbon air emissions. Waste Exchanges Waste exchanges provide a mechanism by which one company's process waste may become another company's process input (material, fuel, etc.), The major distinction between exchanges is what they exchange. Most waste exchanges in the United states are "information exchanges" or "information clearinghouses." The information clearinghouse is an anonymous listing service for: l.
Waste generators who believe their process byproduct could be of value to another industry, and
2.
companies seeking lower cost process input alternatives to virgin materials.
Lists of available and requested materials are circulated to member companies. Written offers or requests for further information are forwarded to the listing company, which may respond to any or none of the requests. Negotiations, if initiated, may or may not be successful. If negotiations are not successful, the listing may appear again, or may be considered non-productive by the company and can·celled ..A few clearinghouses send follow-up surveys to clients to determine the success of their exchanges. Most, however, only estimate successes from the number of responses to individual listings. Such clearinghouses are nonprofit organizations financed by a local chamber of commerce or trade groups with no mandate to actively initiate contacts or aid in negotiations. Their staffs are small, often consisting of non-technical personnel, some devoting only part of their time to the exchange. Materials exchanges are profit making organizations. They may serve as brokers, actively seeking transfer opportunities, and aiding in negotiations between potential exchange partLers, charging a commission and providing laboratory testing for quality assurance. Some material exchanges purchase materials outright, carry out any necessary treatments, and resell the original or treated product when the opportunity arises. -7-
Most of these exchan ges serve the genera l public , except for the Invest ment Recove ry Depart ment of Union Carbid e which runs a single compan y materi al exchan ge. It is a for-pr ofit-m aterial sexchan ge that limits client s to Union Carbid e Divisio ns. An update d list, compil ed and circula ted by the Piedmo nt Waste Exchan ge (7), was used in our phone survey of waste exchan ges to ascert ain curren tly operat ing organi zation s and the approp riate conta ct. Succe ss estim ates as well as past listin gs were reques ted. Inform ation exchan ges are not inform ed of succes sful materi al trans fers. so, with the except ion of those exchan ges that perfor med follow up survey s, no inform ation on what types or volume s of mater ials were actual ly transfe rred was availa ble. Most of the indivi duals contac ted were of the opinio n that contin uous suppli es of liquid hydroc arbon wastes , 'of suffic ient quanti ty and fuel value, could be econom ically transfe rred. This is verifie d by the large number of listing s by recycl ers lookin g for such comm odities . Gener ally, fewer such mater ials are expect ed to be offere d in the future. since once a match betwee n a continu ous suppli er and user is made, the materi al is no longer listed . In additi on, larger compa nies are findin g it more econom ical to recycl e their own solven ts on site or throug h a privat e contra ctor. This trend to recycl e is partic ularly strong in the paint and varnis h indust ry. The use of inform ation from waste exchan ges was limited except for establ ishing genera l trends . Source s, and often exact conten t of wastes , offere d for exchan ge were propri etary. From talking to person nel involve d in waste exchan ges and. compar ing offerin gs and materi als sought , some conclu sions regard ing the curren t "marke t" for waste liquid hydroc arbons can be drawn. Non-h alogen ated hydroc arbons are in higher demand that haloge nated hydroc arbons becaus e of their potent ial as fuels. Other inform ation from the waste follow ing:
exchan ges
includ ed the
l.
Larger quant ities of waste availa ble on a continu ous basis have the best chance for finding a user.
2.
The paint produc ing indust ry has recent ly taken steps. to reduce the amoun t of waste solve nts throug h recycl ing effort s.
3.
The ink produc ing indust ry is changi ng, when possib le, to water based inks reducin g liquid organi c wastes .
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4.
Exchanges usually take more than 90 days to complete a transaction. Under RCRA, holding a hazardous waste over 90 days requires additional permitting, thus inhibiting waste exchanges.
Appendix B contains a summary of information obtained from waste exchange telephone interviews. U.S. EPA Regional Offices In 1980, the U.S. EPA defined hazardous waste and set standards for handling of such wastes (8). Initially, it was the responsibility of the Regional EPA offices to see that states complied with federal guidelines; it was intended that, as each state developed its own confirming hazardous waste program, responsibility would be relinquished by the region to the states. Many of the states have since become responsible for their own programs, leaving the regional offices with a monitoring function. Due to the planned transfer of responsibility to the states and agency budget cuts, Regional EPA Offices have not been tracking hazardous waste manifests. Although states have collected and reviewed hazardous waste information and the forms are available for viewing, the information has not been compiled by most states. At this time, information from the Waste Manifest System is in a usable form in only a few states. California is one state where this information is available; at this time, the state cannot meet the demand for this information and is not presently releasing it. According to the waste manifest information, California can generally require a waste producer to justify his choice of disposal method over recycling. If it is deemed that a material can be recycled, a tax on landfill disposal can be imposed. The results of regional provided in Appendix c.
u.s.
u.s.
EPA office telephone interviews are
EPA Office of Solid Waste
The project team spent a significant amount of time discussing "hazardous" waste hydrocarbon streams with the u.s. EPA Office of Solid Waste. Perhaps some of the most comprehensive and useful information can come from data presently being developed by that office. Unfortunately, much of this information is not presently in a usable form and some will probably be withheld as confidential information.
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The EPA is presently gathering the following informatio n that would have been an important resource in preparing this report, if i t has been available . The reader is referred to these studies, which should be available in the next several months. 1.
Survey of organic chemical producers and manufactu rers on the types and quantitie s of waste generated . A study on the petroleum industry is just getting started. 2.
Survey of facilitie s blending and burning hazardous waste fuels including used oils.
3.
study on solvent use and waste productio n.
4.
One EPA staff member is presently investiga ting those waste streams that are now being recycled . A comprehen sive report is being prepared.
Appendix A contains a compilatio n of informatio n regarding liquid hydrocarb on waste streams and/or by products from one 1981 final report and two draft documents prepared for the u.s. EPA; as such, much of this informati on is subject to change. It is difficul t to predict the influence of RCRA on these streams. Certainl y RCRA. regulatio ns encourage better accountin g and practice s which will eliminat e these wastes or result in recycling . No informatio n was available regarding which of these streams are currently being disposed of, reused or treated. Trade Associati ons Contacts made with major trade associatio ns resulted in no hard data. When questione d about volumes of waste hydrocarb ons their properti es, or present uses, associati on officials almost universa lly referred to current and earlier u.s. EPA surveys discussed elsewhere in this section and hazardous wastes listed in 40 CFR Part 261. Trade associatio ns apparentl y do not compile data on wastes generated by their members. The few specific waste hydrocarb on streams which were noted in these contacts are listed below (suppleme nted with some outside data): waste hydrocarb on
comments
Petroleum refinery residues and slop oils, including API separator sludge (EPA No. K05l). Little is known about aqueous suspensio ns and emulsions recovered during crude oil productio n.
Many residues and slops are nor being landfarme d or returned to refinery processes (9, 10). Also see Appendix A, reference D and reference (11). -10-
waste hydrocarbon
comments
Coal tars; decanter sludge from coking operations (EPA No. K087).
Reasonable value was being obtained for most coal tars and light oils in 1976 (see ~able 1) . Decanter sludges are available for recycling-see Appendix A, Reference D.
Interface oils available from pipelines.
Now being sold to reprocessors for fuel recovery.
Used motor oils from diesel and gasoline engines. Total volume 0.4 billion gallons in 1980.
Now being sold to recyclers. See reference {2) for further information.
Methane from anaerobic digesters and skimmed oil and greases from influent wastewater in municipal wastewater plants.
Only a very small fraction of the wastewater treatment plants make use of the methane gas. Methane can be burned to heat the digesters, fuel engines, or sold to industry. The skimmed oil and greases are generally landfilled. About 15,000 treatment plants in the u.s. have capacity greater than 1 MGD. Perhaps one half of the plants have anaerobic digesters.
Used engine oil and transmission fluid from wrecked autos and trucks. The waste oil generated just from wrecked automobiles is approximatel y 14,000,000 to 20,000,000 gallons a year. Waste auto and truck tires are an additional potential waste hydrocarbon source.
on the average, each wrecked vehicle purchased by an auto recycler generates four to five quarts of engine oil and four to five quarts transmission fluid. About seven to eight million cars are purchased by auto recyclers each year.
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Table 1 COAL TAR CHEMICALS 1976 DATA (12)
Produced, 1000 gal Equivalent Heating Value, billion BTU Yield, gal per short ton coat coked Disposition By Producer Processed, 1000 gal Sold For Refining, 1000 Used As Fuel, 1000 gal Other, 1000 gal Products Produced
Crude Tar** 636,282 95 '45 7 7.60 163,051 290,536 187,526 5 460 646,573
Intermediate Light Oil 5,419
Light Oil 198,056 25,742 2.53
1 '923
89,841 104,645
1,923
194,486
2,482 5,678 516
•
60' 411 8,824 1,496 1 '968 3 993 76,692 0.332 (2 .213)
0.282
0. 502 (3 .860)
0.149 0.377 92.507 0. 794 0.550 0.585 0.398 0.361
*
Includes creosote oil, cresols, cresylic acid, naphthalene, phenol, refined tar, tar paint. Quantity not available. Value equal to $15,079,000 in 1976.
+
Compared to $1.685/MM BTU for coal, $1.628/MM BTU for coke breeze, and $2.38/MM BTU for petroleum distillate in 1976 (14).
**
See reference (13) for typical composition data.
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Waste Hydrocarbon Inventory In spite of the difficulties encountered in gathering data on waste hydrocarbons, a compilation of 174 streams was gathered and is provided in Appendix A. These streams arise from a wide variety of sources and appear in many forms, very often in aqueous solutions, emulsions, and suspensions containing more than 50% water as shown in the following summary: Millions of BTU/hr
FROM APPENDIX A COMPILATION 99-99.9% 90-99 50-90 20-50 10-20 <10
13 2,213 4,179 147 134 5,458 12,144
USED OIL GENERATION (2) Lubes (generally less than 10% water) Other (usually 10-90% water)+
14,000 24,000
The high water content make many of these waste hydrocarbons very difficult to recover. From the perspective of potential research and development programs leading to the possibilities of recovery and reuse, it is useful to know that 23 of the 174 streams identified contain about 79% of the total heating v~lue. These 23 streams are compiled in Table 2.
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Table 2 MOST SIGNIFI CANT WASTE STREAMS ITEM DESCRIPTION* 11 Methyl P-form yl Benzoa te from p-Xyle ne Oxid. 13 Mixed Alkyl Benzen es from Benzen e Alkyl. 14 Heavy Ends from Ethylen e Glycol Monobu tyl Ether Prod. 27 Mixed A~eous Organi c Acids from Cycloh exane oxid. 70 Haloge nated and Nonhal ogenate d Solven ts from Machin ery Ind. 71 Haloge nated and Nonhal ogenate d Solven ts from Electr onic Ind. 73 Solven ts from Paint and Allied Prod. Ind. 75 Nonhal ogenate d Solven ts from Medici nal/ . Botani cal Ind. 79 Hydroc arbon Still Bottom s from Plastic s Inc. 92 organi c contam inated water from Plastic s Inc. 94 organi c Contam inated water from Acrylo nitrile Prod. 105 organi c Contam inated water from Ethyle ne Prod. 106 Organi c Contam inated Water from Ethyle ne Prod. 108 organi c contam inated Water from Phenol Prod. 116 Organi c Contam inated water from Pestic ide Prod. 117 organi c contam inated Water from Pestic ide Prod. 122 Spent Tetrac hloroe thylen e Solven t 143 Distil lation Bottom s from Phenol Prod. 151 Waste Hydroc arbons from Benzen e Prod. 152 waste Organi cs from Acetic Acid Prod. 164 Waste Organi cs from Toluen e Diisoc yanate Prod. 168 Distil lation Bottom s from Benzen e Sulfon ate Prod. 170 Waste Hydroc arbons from Coke Prod.
*
Millio ns BTU/hr 383 506 160 423 100 177 247 266
118 105 689 685 472 121 1985 1624 253 403 101 243 299 128 142 9540
See Appen dix A for furthe r detail under the item number s shown.
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ALTERNATIVE USES The best alternative uses for waste hydrocarbon streams will ultimately depend upon an economic evaluation dealing with the following elements: availability of adequate volume sources, the value of the recovered hydrocarbon for the proposed alternative use, the cost of hydrocarbon recovery and purification, the cost of transportation and handling, the cost of disposal, uses,
or value for other alternative
plus consideration of less tangible factors, which may include avoidance of risk associated with disposal and national policy concerning the conservation of natural resources. Each evaluation to determine optimum alternatives will invariably depend upon site specific circumstances. Although economic evaluation to determine optimum alternatives is beyond the scope of this study, generalizations can be made which should be useful as a rough screening tool to assess potential alternative uses for important waste hydrocarbon streams identified. The following alternative possibilities will be discussed in subsequent paragraphs of this section. Reduce generation of waste hydrocarbons reuse waste
hydrocarbo~s
for their original.purpose
use waste hydrocarbons as a fuel use waste hydrocarbons as a chemical, petrochemical, or fuel process raw material use waste hydrocarbons as a component in construction materials The focus for each of the following discussions is on promising research and development possibilities, rather than immediate proven opportunities for recycle which would most likely already have been· implemented if they did exist. As a matter of fact, the history of the petroleum, chemical and related industries abounds with examples of byproducts for which important uses have been found ( 10, 17, 18, 19, 20) . It also follows from this analysis that the recycle of waste hydrocarbons, i.e. those for which an economic use is not now available, is likely to require the development of new technologies, or at least the application of existing technologies to new situations.
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Reduced Generatio n As discussed in the previous section of this report, reduced generatio n of waste hydrocarb ons often means improving chemical reaction yields andjor selectivi ty or minimizin g product losses in separatio n processes . However, it may also involve minimizin g or eliminatin g the use of solvents or other non-react ants; e.g. in chemical processe s, in the applicati on of coatings, in lubricatio n, in hydraulic systems, and in cleaning operation s. Improving yields, selective ly, and recovery in reactions is highly specific to individua l industria l problems and probably not an appropri ate objective for general R&D studies on waste hydrocar bon recycle. However, as will be discussed in the Research and Developm ent Possibil ities section, there are opportun ities for improving coating, lubricatio n, and hydraulic systems to minimize waste hydrocarb on generatio n. Following are some examples where waste hydrocarb on generatio n could possibly be reduced by improved technolog y: waste hydrocarb on (item no. from Appendix Al Item 21, styrene and byproduct s from manufactu re of styrene
quantity MT/Yr MMBTU/hr 1,816 8
generatio n mechanism byproduct formation
Item 31, dimethyl terephtha late and byproduct s from manufactu re of dimethyl terephtha late
13,620
37
byproduct formation
Item 58, halogenat ed solvents
99,000
74.8
solvents used in degreasin g operation s
Item 70, halogenat ed/ nonhaloge nated solvents'
99,414
100
solvents used in machinery manufactu re
Item 71, halogenat ed; nonhaloge nated solvents
175,827
177
solvents used in electroni c component s manufactu re
70,004
247
solvents generated from paint production
Item 73, solvents
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waste hydrocarbon (item no. from Appendix Al Item 101, dichloroethane in wastewater from dichloroetha ne manufacture
quantity MMBTU/hr MT/Yr 93 172,500
generation mechanism dichloroetha ne loss in wastewater
Reuse Reuse of waste hydrocarbon s is generally limited to their generation in the following situation: less than 100% conversion of reactants occurrence of off-specific ation products by faulty processing, inadvertent contaminatio n, recovery from spills contaminatio n during use, e.g. as commonly occurs with solvents, lubricating oils, greases, hydraulic oils, and other fluids Where volumes of waste hydrocarbon s are sufficiently large, recycling near the point of generation should be considered. As will be discussed in the next section, recycling processes for this purpose may require a specific design for a particular situation or more general types of recycling processes can be used for solvent and oil purification . Reuse near the point of waste hydrocarbon generation is already widely practiced in industry, e.g. in recycle reaction systems, solvent reclaiming, and lubricating and hydraulic oil purification . Very often waste hydrocarbons are transported to a remote site for recycle, e.g. by re-refining or reclamation . Such arrangements can be based on a closed loop, returning a purified product for reuse; or ownership of the waste hydrocarbon stream can be transferred to the recycling plant and recovered products sold into general commerce. Although arrangements for both in-plant and remote recycling are in common use, there are many additional opportunit ies, especially for learning how to handle more complex waste hydrocarbon s. Waste hydrocarbon s found in aqueous solutions, emulsions, and suspensions provide important opportunitie s for recycling.
-17-
Exam ples of waste hydro carbon where new or improv ed techno logy could make reuse possi ble are: waste hydro carbon (item no. from Appen dix A) Item 80, still bottom s from synth etic rubbe r plant s Item 48, waste oil from urea produ ction
quant ity MT/Yr MMBTU/hr 20,341 82
9,080
33
poten tial use recov ery of reacta nts for reuse as raw mater ials recov ery from 80% oil/20 % water and reclam ation
Also see items 21, 31, 70, 71, and 73 from the previo us sectio n on reduce d gener ation. Fuels Virtu ally any waste hydro carbon could theor etical ly be consid ered for fuel use, as indivi dual stream s, in combi nation with other waste hydro carbo ns, or mixed with conve ntiona l fuels. A recen t EPA surve y has shown almos t one billio n gallo ns per year of hazard ous waste burned by gener ators, and nearly an equal amoun t burned in dispo sal/re cyclin g facil ities (21). The fuel value of these waste is not now availa ble. Use of waste hydroc arbon' s as fuels in aspha lt plant s and cemen t kilns is common (20,22 ), but specu lation about possi ble risks assoc iated with the latte r appli cation has recen tly been raised (23). There are many const raints which affec t the succe ssful combu stion of waste hydro carbon s to recov ery energ y. Some of these are: RCRA regul ations which apply to combu stion of hazard ous waste (addi tional u.s. EPA regul ations conce rning used and waste oils are expec ted in the near future ) . Im~ur~ties in the waste hydro carbon s which cause air em~ss~ons--e.g. inorg anics ; compo unds which conta
in halid es, sulfu r, phosp horou s and other eleme nts which lead to acid gases and other undes irable emiss ions; compo unds which are diffic ult to destru ct (24, 25). High water conte nts in many waste hydro carbon s which reduce the heatin g value , frequ ently to the exten t that combu stion canno t be sustai ned andjo r signi fican t heat recov ery is not possi ble. Varyin g compo sition of some waste hydro carbon s so as to interf ere with effec tive do.sig n and opera tion. -18-
All of these constraints can be overcome. The technology needed to do so presents R&D opportunities discussed later in this report. The energy conversion potential of selected industrial waste streams has been previously studied (26). Many unusual liquid organic materials have been used as a fuel for internal combustion engines, usually as a mixture with conventional gasolines. These include alcohols (27) and other oxygenated compounds. recovered waste hydrocarbons can be considered for this purpose if the quantities are sufficiently large and assured, but complex quality problems must be dealt with. Some of the waste hydrocarbons which have been identified which should be susceptible to combustion with heat recovery are: waste hydrocarbon quantity (item no. from MMBTU/hr MT/Yr Appendix A) 8 1,816 Item 21 1 18 1 000 BTU/lb styrene and byproducts from styrene manufacture
comments unconverted styrene and byproducts
Item 130 1 10,886 BTUjlb sludge
29 1 000
79
sludge from paint application
Item 168, 11,618 BTU/lb distillation bottoms
43,650
128
28,224 Item 76, 10,000 BTU/lb organic chemical residues from medicinals
71
Item 164 1 11,015 BTU/lb distillation bottoms
107,900
229
byproduct from alkyl benzene sulfonate production tars, still bottom, sludges formed during manufacturing liquid suspension from toluene diisocyanate production
Chemical/Petrochem ical/Other Raw Materials There would be many opportunities to use waste hydrocarbons as raw materials if specific compounds could be recovered and purified to meet normal commercial specifications. However, there are also potential opportunities for using selected waste hydrocarbons for some petrochemical and petroleum refining processes which normally use complex petroleum hydrocarbon mixtures as a feedstock. This potential for using existing processes will be more fully explored in the following section which deals with Feasible Processes. -19-
The presenc e of halides and certain other elements or high ash content s in waste hydroca rbons could rule them out for use in a normal petroche mical or petroleu m plant because of corrosio n or catalys t poisoni ng, but special faciliti es dedicate d to waste hydroca rbons could be conside red. Even aqueous waste hydroca rbons could be conside red as potenti al feedsto cks for special ly designe d steam cracking or steam reformin g processe s. It seems unlikely that any small volume waste hydroca rbon streams could be conside red as a chemica l/petroc hemical raw materia l because of the complex ity and high capital cost required for such process es.- Some of the larger volume waste hydroca rbons which could be conside red are: waste hydroca rbon (item no. from Appendi x Al Item 134, heavy ends from ethylene dichlor ide product ion
quantity MT/Yr MMBTU/hr 80,000 81
Item 125, spent solvent
15,000
51
Item 79, still bottoms from polypro pylene, polysty rene and coumari n process es
29,204
118
Item 133, chlorina ted hydroca rbons from fraction ating column
35,400
25
mixed chlorin ated hydroca rbons from ethyl chloride product ion availab le for recovery
Item 8, waste solvent from cyanuri c chloride product ion
17,252
71
50% toluene and 35% xylene mixture availab le for recovery or refining to gasoline
Item 84, fish plant effluen t
14,000
18
crude protein and oil can be used to produce proteino us meat and fatty oil
-20-
comment s mixed chlorina ted hydrocar bon 80% toluene in spent solvent availab le for recovery heptane , xylene, cyclohex ane, other hydroca rbons availab le for recovery
Construction Industry Some waste hydrocarbons have been successfully used in roofing and road asphalts. Waste hydrocarbons have long been used for road oiling and dust control, but such use is now considered unacceptabl e in most of the u.s. for environment al reasons. Burning waste hydrocarbons as a fuel in asphalt plants and cement kilns has been previously noted. Wider use of waste hydrocarbon s in asphalt appears to be an attractive possibility , but neither environmenta l concerns nor process and product variables have been fully evaluated to define the limits or the optimum methods for such use. Following are two waste hydrocarbons which could be considered: waste hydrocarbon (item no. from Appendix Al Item 173, acid tar
Used oil vacuum distillation bottoms
quantity MMBTU/hr MT/Yr 69 32,000
10,000
43
-21-
comments from the use of acid in used oil rerefining-feasibility shown by DOE study (28) from re-refining processes for use in asphalts
FEASIBLE PROCESSES This secti on deals with exist ing facil ities and proce could be used for recyc le of waste hydro carbo ns. Re-resses which finin g and conv entio nal petro chem ical and petro leum refin ing proce sses are consi dered . Based on the large quan tities of aqueo us hydro wast es iden tifie d, proce sses which deal with the separ carbo n ation of hydro carbo ns from water are parti cular ly impo rtant. Re-R efinin g and Repro cessi ng Indus try The re-re finin g port ion of this indu stry has unde rgone a revol ution ary chang e durin g the past 10-20 years . Wher eas as many as 150 smal l re-re finer s proce ssed over 300 milli on gallo ns of used oil in 1960 to produ ce lubri catin g oils by acid /clay treat ment and othe r proc esses , there are today less than one dozen true re-re fine rs proc essin g subs tanti al less than 100 milli on gallo ns. The moder n re-re finer y in the U.S. invar iably uses a form of dist illat ion follo wed by a lubr icati on oil finis hing proce ss. On the other hand, large volum es of used oils and waste now being repro cesse d for fuel use or used direc tly as oils are most insta nces repro cessi ng cons ists simpl y of settl ing fuels . In with .or witho ut the use of chem ical addit ives. In a few in tanks insta nces cent rifug es or therm al dehy drato rs are used to supp leme nt settl ing facil ities . · The follo wing step s are comm on to most mode rn re-re finin g proce sses in the u.s. 1.
Settl ing
2.
A flash tower for therm al dehy dratio n and separ ation of a light fuel fract ion
3.
Vacuu m dist illat ion to recov er one or more crude lubri catin g oil fract ions
4.
Clay cont actin g/fil trati on or hydr otrea ting to finis the crude lubri catin g oil by impro ving color and odor h
Exis ting facil ities of this type could be used to recov er some waste hydro carbo n stream s other than used oil. This migh t inclu de aqueo us waste hydro carbo ns provi ded that water conc entra tion is less than about 30% or that emuls ions could be broke n to reduc e feedw ater to that level . The produ ction of purif ied hydro would gene rally requ ire addit ional disti llati on facil carbo ns ities not norm ally found in re-re finer ies.
-22-
The use of re-refining facilities for waste hydrocarbon recovery and purification has several serious drawbacks which make such an approach unlikely. These drawbacks include the following: there is little total excess capacity in the rerefining industry simply because there are so few plants. it is anticipated that the excess capacity which is available because of the diversion of used oils to fuel use will disappear as additional restrictions are placed on burning used oils by state regulatory agencies and the U.S. EPA. it is anticipated that new re-refining facilities will be built, but that these will have an assured feed supply for economic reasons and because of burning restrictions. distillation in existing re-refining plants is not designed for making the sharp separations necessary to recover pure components which may have attractive value from complex mixtures. Therefore, the value of the recovered mixture will be close to that for fuel, not enough to pay for the processing involved unless the waste hydrocarbon feed cost is very low or negative, inclusive of transportation costs. processing of waste hydrocarbons that are classified as hazardous under RCRA or state regulations will require a hazardous waste treatment permit for the particular operations contemplated. Some re-refiners might be willing to pursue such a permit, a complex and costly procedure, but only if used oil supply is short, or if and when similar permits ·are required for processing used oil. re-refining plants generally do not have wastewater treatment facilities which will remove soluble organic chemicals. Thus they cannot handle aqueous water soluble waste hydrocarbons, even where solubility is low, e.g. 0.1% (1000 ppm). Reprocessing facilities, which depend primarily on oiljwater separation by settling andjor centrifugation, are now used to recover waste hydrocarbons for fuel use. It is anticipated that this practice will continue, but that new burning regulations for used and waste oils will require additional process steps beyond the technical and financial capability of typical reprocessing operators. Under these circumstances used oil will be directed toward re-refining, as previously discussed, and other aqueous waste hydrocarbons will require disposal or more sophisticated recycling techniques by processes such as those suggested in the Research and Development Possibilities Section.
-23-
Virgin Petrol eum Refin ing Indus try Althou gh there has been a justif ied reluct ance to introd uce waste hydro carbo ns into exist ing petrol eum refin eries becau se of poten tial catal yst and produ ct conta minat ion probl ems, many aspec ts of the petrol eum proce ss techno logy develo ped during the past 80+ years could be used for waste hydro carbon recyc ling (1). Brief descr iption s of some poten tially appli cable proce sses follow and overa ll proce ssing schem es are discu ssed in the Resea rch and Develo pment Possi biliti es Sectio n. Atmos pheric Disti llatio n. The initia l distil lation proce ss in a petro leum refin ery which separ ates crude oil into relati vely light fracti ons (e.g. flash gas, naphth a, keros ine, diese l and gas oils for crack ing) and a bottom s cut which is fedoil, to vacuum distil latio n. Simil ar distil latio n proce sses could be used to recov ery waste hydro carbon fracti ons from compl ex mixtu res. Vacuu m Dist illati on. Sepa rates atmo spher ic botto ms into addit ional crack ing feeds tock and. a bottom s residu um ·fract which is used as an aspha lt base stock or fed to a residuion um conve rsion proce ss. A simil ar proce ss is alread y in use in moder n re-re finer ies, as previo usly discus sed .. Residu um Proce ssing . The vacuum disti llatio n residu um can proce ssed in a varie ty of ways depen ding upon the nature of be the crude oil and the refin ery produ ct mix requi red. Avail able residu um proce sses includ e: deasp haltin g by solve nt extrac tion to produ ce eithe r lubri catio n oil brigh t stocks or crack ing feedst ocks plus speci ficati on aspha lts. visbr eakin g (mild crack ing) to produ ce midd le disti llate s and reduc e residu um visco sity, decre asing cutte r stock requir ed for heavy fuel oil blend ing. coking involv es crack ing residu um to crude gaseo us and liqui d produ cts plus coke in a batch delaye d coking proce ss or a conti nuou s fluid ized bed coker . In modi ficati ons of the fluidi zed bed, the coke can be gasifi ed with steam to produ ce fuel gas, or synth esis gas for metha nol, ammon ia or hydrog en produ ction. Crack ing. Petrol eum fracti ons rangin g from gas oils to heavy oils are cracke d to produ ce gasol ine and middl e distil lates (with some fuel gas produ ction) . Fluid ized bed cracki ng with cataly sts is the most common approa ch.
-24-
ct Arom atics Extra ction. A varie ty of solve nts are used to extra atic arom ce produ arom atics from petro leum fract ions to ine petroc hemic als or aroma tic conce ntrate s as a high octane gasol some In ate. blend ing stock , leavi ng a low aroma tic raffin low insta nces the prima ry objec tive is the manuf acture of the nents, compo aroma tic raffin ates as speci alty solve nts, jet fuel and high-s moke point keros ines and diese l fuels. in Octan e Impro vemen t. A varie ty of catal ytic proce sses are used e octan refin eries to produ ce compo unds which improv e gasol ine fin numbe r. These includ e proce sses which produ ce branch ed paraf ce produ isome rs (isom eriza tion and akaly lation ), those which ce high produ which those and , ing) reform arom atics (cata lytic octan e fracti ons from light olefin s (dime rizatio n) . en, Hydro treatin g. Catal ytic proce sses which remov e sulfu r, nitrog by ons fracti eum petrol of ty varie wide odor, and color from a reacti ons with hydrog en at high tempe rature and pressu re. Chem ical Treat ment. Petrol eum fracti ons are treate d with acid, by caust ic, or water solut ions to remov e impur ities, follow ed Deery. recov on fracti eum separ ation of the two phase s and petro'l ce emuls ificat ion in an elect rical field is commo nly used to enhan the separ ation. Fluid ized Bed Incin eratio n .. This type of incin eratio n has been of devel oped as a multi ple use flexi ble means for dispo sing ery recov refine ry waste stream s offeri ng the poten tial for energy ( 2 9) •
Chem ical/P etroch emica l Indus try a In a simil ar fashio n to the situat ion in petrol eum refini ng,for large reser voir of techn ology is poten tially avail able able proce ssing waste hydro carbon s. Only the most gener ally applic . for prepa ration of marke table raw mater ials are discu ssed below Pyrol ysis. Pyrol ysis in the petroc hemic al indus try usual ly refers to the crack ing of petro leum fracti ons under condi tions which lene favor olefi n forma tion, most commo nly ethyl ene and propymost In rials. mate raw ical which are impo rtant petro chem comm ercial proce sses, the crack ing takes place in furnac e tubes on in the presen ce of steam , with heat for the endoth ermic reacti have sses proce Other . suppl ied indire ctly throug h the tube walls e been devel oped, parti cular ly for residu al oils, which utilizto r, heate al extern adiab atic reacto rs or fluidi zed beds with an and produ ce olefin ic produ cts (30, 31, 32, 33). both the tubul sar with carbon hydro non-t ubula r reacto rs could be adapte d to waste r or witho ut a reaso nable water conte nt, but the non-t ubula such ities impur system s would be most suitab le to mixtu res with as ash.
-25-
Part ial Oxid ation . The reac tion of oxyg en/st eam mixt ures with petro leum frac tion s is used to prod uce hydr ogen jcarb on mono xide mixt ures . Feed stock can rang e from natu ral gas throu gh resid ual and crud e oil. Hyd roge n/ca rbon mono xide mixt ures are used to prod uce hydr ogen , amm onia , meth anol , and othe r impo rtant prod ucts. Part ial oxid ation appe ars to be a prim e cand idate for recy cle of wast e hydr ocarb ons. Steam Refo rmin g. Hydr ogen /carb on mono xide mixt ures are also made by cata lyti c steam refo rmin g in furn ace tube s. reac tion is high ly endo therm ic. The high pres This type of reac tion syste m used coul d not be read ily adapsure cata lytic ted to any but vola tile, clean wast e hydr ocarb ons. Add ition al pyro lysis capa city in the u.s. , espe ciall y capa city capa ble of hand ling heav ier hydr ocarb on feed stock fore cast (34). This expa nsion prov ides an oppo rtuni s; has been of wast e hydr ocar bons if the nece ssar y tech ty for the use nolo gy can be deve loped . The ethy lene and prop ylene prod uced are impo rtant raw mat eria ls for poly meri zatio n and othe r impo rtant comm ercia l chem icals . · In-P lant Recy cling Proc esse s A wide vari ety of in-p lant recy cling proc esse s are puri fica tion of lubr icati ng, hydr aulic , and insu being used for solv ent reco very and for oil reco very from oiljw latin g oils , for ater emul sions . A brie f discu ssion of thes e follo ws. The choi ce of in-p lant recla mati on equip ment upon the natu re of the imp uriti es whic h haveobvi ously depe nds duri ng serv ice, by the natu re of the wast e hydr been intro duce d econ omic and phys ical cons idera tions . For exam ocarb on, and by oil may be conta mina ted by part icul ate matt er due ple, lubr icati ng meta l. It is impo rtan t to remo ve thes e part to wear of gear furt her wea r, and beca use the met als mayicle s to redu ce degr adat ion. In such a case it may be nece ssary cata lyze oil filte r, or cent rifug e in orde r to resto re the oil only to sett le, to its orig inal use. If ther e are othe r cont amin ants, they may build up so· slow ly that the oil can be recy cled by part icle sepa ratio n many time s befo re the oil must be disca rded or furth er puri fied . Port able filte rs are often used in plan ts with mult iple oil serv ices wher e part icul ate matt er is the grea test conc ern. In othe r situa tion s, lube oil may be conta mina ted only by wate r, whic h call s for quit e a diffe rent type of recla mati on. Mois ture may be pres ent only in minu te quan titie s, such as in insu latin g oils , in some what larg er qua ntiti es in oils used in outd oor mobi le equip ment , or in subs tanti al quan titie s as emul sions in
-26-
coolants. In many instances, a vacuum still is a useful method for water removal. The reason for the vacuum is, of course, to avoid the necessity for heating the oil as high as the normal boiling point of water (212°F), but also to minimize dissolved air contaminat ion which can cause oil oxidation. Similar equipment can also be used to eliminate light hydrocarbon contaminatio n, for example resulting from seepage of solvents or gasoline past a seal into the lubricating oil. In some instances contaminants may be of an incompatible chemical nature formed by degradation or by reaction with other materials, for example, air or combustion products. In this case, more complex approaches to reclamation may be necessary. Sludges or polymers formed in this way can often be removed by filtration or centrifugati on, but where the polymers or other contaminants are soluble in the hydrocarbon other purification methods must be sought. For example, Fuller's Earth (clay) treatment is used to remove soluble or even insoluble impurities. But additives may also be removed by clay treatment, thus requiring an additive restoration step in some systems. The effectivene ss of clay treatment should be judged by chemical analysis and specificatio n testing, but, in some instances, observation of color and odor can be used for quality control. Treatment temperature is an important variable when clay is used. Ultrafiltrati on, where the membrane filter has pores of molecular size and will pass water but not colloidal and emulsified solids or dissolved macromolecu les, has recently become an important reclamation method. This type of filter is particularly useful for recovering waste hydrocarbons from emulsions(35 ). Recovery From Wastewater As noted earlier, opportuniti es exist for recovery of large quantities of waste hydrocarbon s from aqueous solutions, emulsions, and suspensions . The problems of recovery from solution are by far the most difficult. These will be discussed first, followed by a discussion of processes available for hydrocarbon separation from emulsions and suspensions. Waste Hydrocarbon/ Water Solutions. Distillation , extraction, and adsorption are the classical unit operations which can be used to separate waste hydrocarbons from true solutions in water. Steam, gas, and vacuum stripping can be used for removal of volatile organics. Oxygenated organics and many other waste hydrocarbons from azeotropes with water, making it very difficult to obtain either pure hydrocarbon or pure water streams by simple distillation . This fact, coupled with high energy costs often encountered , make distillation too costly except where the hydrocarbon recovered has substantiall y greater than fuel value. However, separation processes can sometimes be justified by the need to purify the water for discharge and/or the avoidance of disposal costs. -27-
Membrane processes can be considered in some instances, but cost, membrane life, and the need to dispose of a byproduct aqueous stream has a dampening effect .on this approach. Evaporation of a portion of the water to produce a concentrated aqueous stream of about 25-30% hydrocarbon or more can produce a material potentially useful as a fuel. However, even in this case the evaporated water may contain environment ally undesirable hydrocarbon. Regenerable desiccant can generally be used for water removal, or even non-regene rable desiccants for removal of very small quantities of water, but costs are high. Waste Hydrocarbon/ Water Emulsions and Suspensions. As compared to waste hydrocarbon solutions, emulsions and suspensions can be treated more readily to recover hydrocarbons . But even here, the type of hydrocarbon and its solubility is important because of the residual hydrocarbon content in the water phase which is proportiona l to its solubility. Gravity settling in empty and baffled tanks or lagoons is commonly practiced, but tight emulsions may require chemical additives andjor heat to break the emulsion. Polymers, alum, ferric salts, acids, sodium ~ilicates, and other chemical additives are often used for this purpose. Skimming devices are usually required for hydrocarbon recovery. The water content of the recovered hydrocarbon is dependent on the efficiency of the skimming device. Settling can be enhanced by the use of centrifuges with or without additives and heat. Dissolved air flotation with or without additives is an alternative method for hydrocarbon/ water separation (36). ~iltration
can also be used to separate insoluble hydrocarbons from water. The use of ultrafiltra tion membranes is very effective for emulsions providing that there is no detrimental effect of the hydrocarbons on the membrane to be used (35, 36). Ultrafiltrat ion can produce relatively clean water suitable for discharge to a sanitary sewer plus a recovered hydrocarbon concentrate containing up to 60% oil and solids admixed with water. As with solutions, the use of desiccants is also possible. Recovery From Air Emissions The subject of hydrocarbon losses to the atmosphere is not within the original scope of the studi•s reported here. However,· recovery of these waste hydrocarbon s does represent a major potential conservation measure, as well as a means for preventing environment al degradation. A total of approximatel y 28 million metric tons (probably more than 0.6 quads) per year of hydrocarbon s are lost to the atmosphere. Losses occur from vehicles, stationary combustion , a variety of industrial processes, and miscellaneou s sources. Each of these sources and their control are outlined below. A much more detailed discussion of this subject appears in a 1982 EPA study (37).
-28-
Automotive Combustion. About 11 million metric tons per year of hydrocarbon s are emitted from vehicles (38). Pollution control involves either recycle to the engine or combustion to co and H20. Recovery in the context of this study does not 2 seem possible. Stationary Combustion. About 1.4 million metric tons per year of hydrocarbon s are emitted from all stationary fuel combustion sources (38). Control is normally by more efficient combustion. Industrial Sources. About 10.5 million metric tons per year of hydrocarbon s are emitted from other industrial sources (38), including 4 million from solvent use. A variety of control methods are in use, ranging from destruction by incineration to control by absorption, condensation , adsorption, conservation , and other methods. Hydrocarbon emission control is becoming more stringent, increasing opportuniti es for recovery. Improved technology would enhance these opportunitie s. Miscellaneo us Sources. Of 4.4 million metric tons per year emitted from miscellaneou s sources, 3.4 million are from organic soivent use, e.g. surface coating, degreasing, dry cleaning, printing, publishing and others. The control methods cited above, including alternative processes and conservatio n, are all applicable. · Other Feasible Processes As discussed in the Alternative uses Section, there are potential outlets for waste hydrocarbons in the construction industry. For example, re-refining vacuum distillation bottoms have already been used to some extent in asphalts. U.S. DOE studies have shown possibilitie s for acid sludge utilization in bricks and paving materials ( 28, 39) and distillation bottoms utilization as an asphalt component (39) . Although these specific studies dealt with used lubricating oil recycling, they also may have application to other similar waste hydrocarbons .
-29-
RESEARCH AND DEVELOPMENT POSSIBILITIES The escalating cost of waste hydrocarbon disposal has provided considerable incentive for research and development on recycling means and alternative forms of disposal. Inevitably, the easiest and most prevalent problems are solved first, leaving the difficult wastes for continued disposal by landfill, incineration, and other available means. It is the intent of the following discussion to especially concentrate on research and development which is not being pursued and is unlikely to be pursued in the near future. Combustion There has been continuous improvement in burners and combustion controls which allow a wide variety of waste hydrocarbons to be burned alone or in combination with conventional fuels (40,41). In addition, the u.s. EPA has undertaken a major research and development program to define combustion conditions which will insure that hazardous wastes can be burned with destruction efficiencies meeting RCRA requirements (42). Air pollution controls are available to handle almost any type of emission, but opportunities still do exist for more effective and more economica.l controls (43). Compiled below are several combustion system research and development needs, suggested by the results of this study, where there is no evidence of comprehensive programs in place to meet those needs. l.
Methods and materials useful for heat recovery when burning waste hydrocarbons containing halides and other precursors of corrosive combustion products. Boiler secondary economizers with tubes protected by coextruded Teflon have recently been introduced to allow heat recovery under acid (and water) condensing conditions(44).
2.
Methods for recovery of potentially valuable elements contained in waste hydrocarbons during combustion, e.g. heavy metals in the ash; halides from the halide acids formed during combustion; and useful compounds of N, P, and s.
Process and Product Modifications Most R&D on process and product modifications are generally best left to the specific suppliers and/or users of the waste hydrocarbons. This is especially true in the area of improving reaction yields and selectivity by modification of catalysts and catalyst systems and optimization of reaction conditions.
-30-
However, there are some universal problems, which could be attacked in a more general way. For example, although some progress has been made, there are further needs for: 1.
Replacement of solvent coating systems with those which do not require liquid solvents, e.g. aqueous, electrostatic, and fluidized bed coating systems; or systems which simply decrease the amount of solvents required (45).
2.
Improved stability (longer life) lubricant and hydraulic oils either by modifying composition or additives.
3.
Replacement of hydraulic oils with aqueous base materials.
Recovery From Aqueous Solutions Distillation is normally the preferred method for separating a true liquid solution into its components. However, two characteristics of most aqueous solutions of waste hydrocarbons make the distillation approach questionable. First, most of the aqueous solutions compiled in Appendix A are very high in water content and low in recoverable organics, thus requiring high energy input per unit of recovered organics for distillation. Even worse, if the organic is less volatile than water, all of the water must be vaporized for separation to take place. second, 'many of the organics in the waste hydrocarbon streams from azeotropes with water making it impossible to recover pure materials by simple distillation. The difficulties in using distillation to purify aqueous solutions of waste hydrocarbons provides incentives for R&D on alternative methods for seapration, e.g. 1.
Improved methods for azeotropic distillation applied specifically to aqueous solutions of waste hydrocarbons.
2.
Waste hydrocarbon recovery by extraction.
3.
Waste hydrocarbon recovery by adsorption.
4.
Low volatility waste hydrocarbon recovery by multiple effect evaporation.
5.
High volatility stripping.
6.
Waste hydrocarbon recovery by membrane processes.
waste hydrocarbon
-31-
recovery
by
Recovery From Aqueous Emulsions and Suspensions As discussed in the previous section of this report, many methods have been developed for separating oil/water mixtures which are applicable to the subject of waste hydrocarbon recovery. However, most of the technology has been directed toward water purification. Improved skimming devices and other methods aimed at recovering a relatively clean and dry hydrocarbon phase would be useful, providing an opportunity for R&D. Recovery From Gaseous Emissions Some of the processes available for recovering waste hydrocarbons from air emissions were discussed in the previous section. Three approaches which' are not now known to be in significant use may warrant further attention. 1.
Recovery of waste hydrocarbons by adsorption, followed by thermal desorption using a minimal volume of hot gas,and incineration of the desorption gas with heat recovery.
2.
Recovery of waste hydrocarbons by adsorption, followed by thermal desorption using a very low volatility liquid, and recovery from the liquid by distillation.
3.
Recovery of waste hydrocarbons by absorption in a very low volatility liquid, and recovery from the liquid by distillation.
Preparation of Chemical and Fuel Raw Materials Basic petroleum refining and chemical processes previously discussed can be adapted to handling waste hydrocarbon streams. All of these would require some R&D effort before their use could be realized. Some of the promising approaches include: 1.
Pyrolysis to prepare olefinic monomers. The use of a fluidized b~d process to convert aqueous solutions appears to be worth further investigation.
2.
Thermal or catalytic cracking to prepare gasoline and heating oil fractions.
3.
Fluidized bed or delayed coking to prepare crude gasoline or heating oil fractions and coke.
4.
steam reforming or partial oxidation to make H2/CO mixtures. These mixtures can then be used to synthesize ammonia, methanol, formaldehyde, or gasoline.
-32-
Longer range approaches should also be considered for converting waste hydrocarbon to useful raw materials, e.g. the development of new cracking catalysts, other Lewis Acid catalysts (such as H2S04, AlCl3, A1Br 3 ), and oxidation catalysts. Integrated Recycling Facilities Some of the proposed R&D work on processes could culminate in the possibility of an integrated recycle facility which could handle virtually any waste hydrocarbon stream. Speculation on such a possibility has resulted in the flow diagram shown in Figure 1. An assessment of technical and economic feasibility for such processes would be a valuable R&D effort. The flow diagram in Figure l represents one possible integrated recycling scheme which could reclaim virtually any waste hydrocarbon stream identified in this study to useful materials, minimizi~g the need for waste disposal. Other schemes are possible, including the use of only a portion of the processes illustrated in Figure 1 for fewer waste hydrocarbon stream types. The flow diagram in Figure 1 is designed to handle: aqueous wastes containing soluble and insoluble light and heavy hydrocarbons nonaqueous waste mixtures of soluble and insoluble light and heavy hydrocarbons waste hydrocarbon steams with a high ash content As shown in Figure 1, the products which could be produced for recycle include: organic compounds which may or may not need further purification before sale as products mixtures of organic compounds useful solvents, or chemical raw materials
as
fuels,
hydrogen and carbon monoxide useful for hydrocarbon synthesis, ammonia synthesis, ·iron ore reduction, hydrotreating, and other purposes energy in the form of steam, electric power, etc.
-33-
:;I ·-----0
"I
'
I
0
- 34 -
Other R&D Possibilities Other R&D possibilities which could improve the potential for recycling are: 1.
An in-depth analysis of U.S. EPA hazardous waste survey data which are just now becoming available. This would require an agreement between DOE and EPA as to the handling and use of the data.
2.
A survey of waste hydrocarbon arising from production of crude petroleum, including new wells, secondary and tertiary recovery, and existing waste oil lagoons. It is believed that this source of waste hydrocarbons is very large, but no data on the subject are known to exist.
3.
Definition of parameters which would allow waste hydrocarbons to be used in roofing and road asphalts.
The following areas have been recommended for further research on recycling waste hydrocarbon liquids in another study of hydrocarbon streams (37): 1.
Control and reclamation of used industrial oil.
2.
Recovery and reuse of used solvents.
3.
Energy Implications of RACT (Reasonably Available Control Technology) for VOC Emission Control.
4.
Reuse of liquid hydrocarbon streams as fuel.
5.
Identification of voc recovery potential from selected solvent use categories.
6.
Identification of VOC recovery potential industrial chemical manufacturing applications.
-35-
from
CURRENT STATUS OF EACH OF THE TWENTY-THREE (23) MOST SIGNIFICANT WASTE HYDROCARBON STREAMS Purp ose An in-d epth inve stiga tion of the twen ty-th ree most sign ifica nt wast e strea ms was perfo rmed to asce rtain the curr ent statu s and mana geme nt prac tice s for thes e strea ms. This was perfo rmed to fac ilita te the DOE 's deli bera tion on futu re rese arch and deve lopm ent fund ing. Meth ods Lite ratu re sour ces avai labl e at both publ ic EPA libra ries were revie wed for more curr ent info rmat ion. and As prov ed inad equa te, a limi ted dire ct indu stria thes e sour ces unde rtake n, using RECON's exte nsiv e indu stria l contl surv ey was of the surv ey are disc usse d in the follo wing acts. Resu lts sect ions and summ arize d in Tabl e 3. Resu lts Pro duc tion of Dim ethy l Tere phth alat e (Item Four man ufac ture rs were surv eyed for info rmat ion abou11). t the wast e strea ms resu lting from this proc rss. Of the four , one did not resp ond, one indi cate d that prod uctio n had ceas ed, and two prov ided some usef ul info rmat ion. The orig inal obta ined for this repo rt indic ated that this wast info rmat ion Meth yl P-for myl Benz oate 83%; Meth yl Hydr ogen Teree strea m was: phth alate 9%; othe r 8%. The larg e perc enta ge of a sing le comp ound good poss ibili ty for recy cle, whic h is what the surv indi cate s a ey conf irme d. Both man ufac turer s that respo nded indic ated that wast e strea ms from this proc ess are recy cled inte rnal ly or sold as inte rme diat es. One man ufac turer send s some of the wast e to anot her plan t of the same pare nt comp any to be recy cled . Prod ucti on of Ethy l Benz ene (Item 13). Five of the seve n man ufac turer s surve yed respo nded . One indic ated that prod uctio n of Ethy l Benz ene was 'disc onti nued . The orig inal info rmat ion obta ined give s wast e com posi tion as: Oiet hylb enze ne 59%; Poly ethy lben zene 11%; S-Bu tylbe nzen e 10%; Alum inum Chlo ride 18%; Othe r 2%. (Volu me of this wast e strea m was given at 136,2 00 MTjYr with a heat ing valu e of 14,76 0 BTU /lb.) The infor mati on prov ided dire ctly by the manu factu one wast e strea m simi lar to the one abov e (if rers indic ated the alum inum chlo ride is disre gard ed) and anot her strea m whic h appe much heav ier cut (aga in with no alum inum chlo ars to be a man ufac ture rs indi cate d high er BTU valu es than ride ). Both were give n prev ious ly. One manu factu rer gave infor mati on on the quan tity of wast e gene rate d and it conf irme d the quan tity prev ious ly repo rted.
-36-
All four manufacturers use the waste as as solvent or heat transfer fluid first, on-site for energy recovery. The second as blend stock for heavy fuel oil. The the fluid internally as fuel. The fourth uses the rest internally as fuel. Composition varies considerably. following waste description:
fuel. The first uses it and then burns the waste sells the waste for use third manufacturer uses sells some as blend and
One manufacturer gives the
tetra-hexa Ethyl Benzenes Ethyl Phenol Ethers miscellaneous high boilers open cup flash point viscosity gross heating value halogen content metals
26% 35% 39% 260°F 45 ssu 19,000 BTU/lb l . 35 weight % <0.0001 weight %
Another manufacturer describes the waste as <60% diethylbenzene with polyethylbenzenes, approximately 18,000 BTU/lb, and no AlC1 3 . Another just describes the stream as polyethylbenzene residues. The third manufacturer gave no detailed waste description. Production of Ethylene Glycol, Glycol Ethers, and Ethanolamines (Item 14) . Only two producers responded, The original information in the report characterized this waste as follows: Heavy ends 98%; Triethylene Glycol 2%; Heaving value 11,944 BTU/lb; 53,118 MT/Yr. Although our industry sources were limited the original information was shown quite incorrect. Our sources indicated a quite different composition. One producer indicated the composition as 60% Triethylene Glycol, 25% Tetraethylene Glycol, and 15% Solids. About 800,000 lbs were sold in 1985, (The heavy ends are sold as product.) The other producer gave no description of the stream as it is combined with other streams and no analysis was available. Adipic Acid from Cyclohexanol oxidation (Item 27). Two manufacturers responded to our survey. One indicated that the information required was publicly available from the EPA, but the EPA currently has a policy of giving out no information. The original information indicated a composition as follows: Succinic Acid 11%; Glutamic Acid 11%; Adipic Acid 11%; Water 67%; 2,263 BTU/lb; 742,744 MT/Yr. The information obtained by survey, information obtained previously.
-37-
in general,
confirms the
The produ cer that respon ded report ed the waste stream compo sition as follow s: 25-35% organ ic; 1-1/2- 2% Nitric Acid; trace cu, u, and Monob asic Acids . curre nt manag ement pract ice is to conce ntrate the stream for sale or use in on-si te power house. It is used for so contr ol. 2 Waste quant ity given by one produ cer (9,000 lbsjhr ) seemed much lower than previo usly repor ted. Manu factur e of Plast ic Mater ials and Resins (Item 79). six of eight manu factur ers respo nded to our survey . One manuf acture grant ed us acces s to the 3007 form filed with the EPA.r Unfo rtuna tely this was not relea sed. The other five provid ed usefu l inform ation . The origi nal inform ation in the repor indic ated a waste stream cons isting of Hepta ne, Xylen t cycloh exane , Propy lene, and other aroma tic hydro carbon s. Heatine, g value was estim ated at 16,00 0 BTU/lb and gener ation at 29,204 MT/Yr . A waste stream quite differ ent from this one was descri bed by the produ cer respon ding to the survey . Three of the respon ding manuf acture rs were produ cers of PVC. produ cers destr oy their solve nt waste via burnin g. one of All manuf acture rs sends these waste solve nts off site to be burned the at a comm ercial incin eratio n facili ty. The other manuf acture r burns these solve nt waste s on-si te in a therm all oxidi zer which burns vinyl chlor ide gas. The third burns his waste s on-si te also in a boile r with heat recov ery (<9,00 0 galjw eek). One of the PVC manuf acture rs chara cteriz ed the waste solve nt as follow s: Water 0-5%; Vinyl Chlor ide 10-20% ; Ethyl Chlor ide 1-2%; trich loroe thyle ne 10-30% ; Tolue ne 50-60% ; quan tity 00 tonsjy r. Anoth er manuf acture r chara cteriz ed the waste as 200-3 Toluen e with other solve nts; this may be essen tially the same waste solve nt as above (and quan tity 1800 galjm o). one of the manuf acture rs descr ibed other waste stream s assoc iated with their PVC manu factur ing proce ss and their respe ctive manuf acturi ng pract ices. Solid PVC is recov ered from the waste stream by a liqui d cyclo ne and then recyc led to produ ct. Lime is used softe n the water . The waste sludg e from this opera tion to is landf illed . All other waste stream s are treate d by biolo gical oxida tion. One of the other manu factur ers in this catego ry makes polym emuls ions (Butad iene, styren e, and Aceta te) . Solid ified mater er and polym erized mater ial is landf i1led offsi te (20-30 % waterial Waste water goes to a settli ng lagoon and is then landfa rmed. ). No inform ation was volun teered as to waste compo sition . A styre ne manu factur er uses vacuum devo latili zatio n to produ cts. vapor s are burne d in a therm al oxidi zer. Heat dry recov ered. Previo us pract ice was to sell tops as resin thinn is for fiber glas s. Comp ositio n is most ly Ethy l Benze er ne, appro ximat ely 19,000 BTU/l b and > 1 mil lbsjy r.
-38-
Toluene and Ethyl Acetate are used to clean kettles used in batch operations. This solvent is sent out to be incinerated for beneficial use. Five of the eight manufacturers in this category have supplied information at this time. Manufacture of Plastic Materials (Item 92). sixteen manufacturers were surveyed in this category. Eleven manufacturers responded. Nine of the manufacturers provided useful information. The original information contained in this report described this waste stream as follows: water 91%; ash 2%; Phenol 5%; Formaldehyde 2%; 861 BTU/lb; 486,000 MT/Yr. Five of the manufacturers gave similar information on the composition. One of the manufacturers does not manufacture phenol-formaldehy de resins; two other manufacturers provided information on their management practices, but not on their waste stream compositions. The five descriptions of the waste stream can be summarized as follows: Phenol 4-5.5%; no ash present; Formaldehyde O.l-0.25%; water makes up balance. One of the producers claims to have 0.1-0.2% phenol-formaldehyd e resin in this stream .. Another claims l. 5% methanol and 1% other organics composed of toluene, benzedioxane, oligomers of phenolformaldehyde, and other hydrocarbons. Quantities ranged from 5-10 gpm (2.5-5.3 mil galjyr). Only three sources volunteered this information. This information. obtained from the survey differs quite substantially from the data originally obtained for the report. No ash was reported present in the was·te stream. The formaldehyde content was reported to be much lower in concentration. Also one manufacturer claimed contaminants that were not mentioned in previous literature. The phenol content was similar to that previously reported. The information provided on the quantity of the waste generated confirms the order of magnitude that was included in the original report summary. Management practices varied considerably. Six of the producers provided information on their current management practices. Two of the respondents discharge this waste stream to sewer; one of these producers first dilutes the waste stream with cooling water to 350 ppm phenol. Two other manufacturers claim no waste from this process. The first claims a ''total recycle'' and the second "no waste" due to a patented process. The remaining three manufacturers outlined their treatment in some detail. One of them performs a phenol extraction in order to recycle the phenol and then sends the remaining waste offsite for incineration. Another manufacturer settles the waste stream and
-39-
remov es the bottom s to be burned in their boile r. Then a liquid liqui d extra ction is perfor med with toluen e; a separ ation via distil latio n follow s. Pheno l is recyc led. The metha nol is used fuel. The resul tant waste water is sent to the local munic as ipal water treatm ent facil ity where it is treate d by biolo gical oxida tion. The third manuf acture r incin erates this stream direc tly witho ut organ ic reclam ation. The manuf acture r that does not produ ce pheno l-form aldehy de resins instea d produ ces liquid resins for adhes ive use. They have a nonhazar dous waste water efflu ent which under goes a deslu dging opera tion. resid ue is landf illed on site and water goes to a fores tation proje ct. There are ppm's of forma ldehyd e in this liquid as forma ldehyd e is used as a prese rvativ e for the produ ct. KO 11, KO 13, KO 14 Prod uct ion Wast es (Item 94) . Three manuf acture rs were survey ed; only one of these manuf acture rs has provi ded inform ation. The inform ation obtain ed in the origin al repo rt descr ibed the waste as follow s: water 98%; ash 2%; Acryl onitri le 0.04% ; cyanid e 0.3%; Aceto nitril e 0.6%; 861 BTU/l b; 3,181 ,000 MT/Yr . It was stated that deep well injec tion is used as the metho d of dispo sal for these waste s and that they conta ined less than 1000 ppm cyani de. Addit ionall y, the waste stream KOll was descr ibed in more detai l as: · Total organ ic carbon Disso lved solids (main ly Ammonium Sulfa te) Inorg anic suspen ded solid s The organ ics are oils
11,000 ppm 108,00 0 mgjl 260 mgjl
conta ining nitrog en.
K013 is descr ibed as: organ ic Disso lved solids Suspe nded Solid s (Ammonium Sulfa te and Organ ic Acid Salts and Organ ic Polym eric Mater ial)
6 1 000 mgjl 5,800 mgjl 20 mgjl
No inform ation was volun teered about quant ities produ ced or fuel value . The infor matio n provi ded about these waste stream indic ated a much highe r organ ic conte nt and gave more detail s ed than previo usly repor ted. Quenc h Blowdo wn from Ethyle ne Produ ction by Therm al crack ing Natur al Gas (Item 105). Only four of the thirte en produ of cers surve yed respo nded. The origi nal inform ation in the repor descr ibed this waste stream as follow s: water 98%; Tolue ne 0.2%;t
-40-
Phenol 0.04%; Benzene 0.8%; 333 BTU/lb; 8,172,000 MT/Yr. Informat ion supplied by one source confirms the high water content and about 1% organics. All responses lacked informatio n on compositio n or magnitude of the waste stream. Only informatio n on managemen t practices was provided and all dealt with the quench blowdown in different manners. One producer adsorbs the organics and recycles this material to the crude unit convenie ntly located on site. Another producer strips organics out of the blowdown before disposal. The third producer has four facilitie s. In three of the facilitie s the quench blowdown is cleaned, and the clean water is used as boiler feed and the organics are incinerate d on site. In the fourth facility the wastewat er is recycled. Organics are removed from the quench via flocculati on followed by skimming. The new facility includes a cracker. Productio n of Phenol (Item 108). The original report informatio n described this waste stream as follows: water 92%; Phenol 2%; 344 BTU/lb; 1,398,000 MT/Yr. Only one producer was surveyed and responded to our question. They indicated that waste is generated containin g phenol at levels of 500-1000 ppm at a rate of about 50 gpm. No recovery is performe d. Our survey indicated a phenol concentra tion 20-40 times lower than we originall y reported. Productio n of Pesticide (ITem 116). Monsanto was surveyed, but no response was obtained at this time. The original report described this waste stream as follows: water 75%; ash 20%; Parathion 3%; 500,000 MT/Yr. Productio n contacteq described Chlordan e the survey
of Pesticide (Item 117). Velsicol Chemical Company was The original report and no response was obtained. this waste stream as follows: water 75%; ash 20%; No informatio n was obtained from 3%; 500,000 MT/Yr. to confirm or disprove this.
Distillat ion Bottoms from Phenol Productio n (Item 143). Ten phenol manufact urers were surveyed and three manufact urers responded . Of the three only two provided useful informati on. The original report described this waste stream as follows: water O%; ash 5%; Phenol 0.9%; Benzo(A) pyrene 0.1%; Benzo(A)A nthrocene 0.1%; Chrysene 0.1%; heating value of 3313 BTU/lb; 26,300 MT/Yr. Informati on provided by the two manufactu rers suggest this waste stream is much larger than previousl y estimated . one facility reported 13.5 mil lbsjyr and the other 35-40 mil lbsjyr. If ten facilitie s still produce phenol, this waste stream is probably greater than 100,000 MT/Yr; much larger than the 26,300 MT/Yr · previousl y estimated .
-41-
A deta iled waste desc ripti on was given by one manu factu rer: Phen ol 5%; Cumy lphen ol 40%; Alph a-Me thyl styre ne Dimer s 25%; Acet ophe none 10%; othe r orga nic comp ound s in very low conc entra tions 20%. Both manu factu rers burn this mate rial in boile rs. One of the manu factu rers proce sses the waste first to recov er some chem ical value befor e using the resid ue as a fuel. Hydr ocarb on Waste s from Benze ne Produ ction (Item 151). Eleve n out of 34 manu factu rers respo nded to the surve y. Of the 11 respo nses five respo nded to inform us that the facil ity no longe r produ ced benz ene. Previ ous liter ature chara cteri zed this waste strea m as follo ws: water O%; ash 5%; Tolue ne 10%; Benze ne 10%; heati ng value of 17,62 4 BTU/ lt; 22,70 0 MT/Y r. Five of the man ufac turer s utili ze a close d loop solv ent extr actio n proc ess. Some wast ewat er is resu ltant from this proce ss, but only with very low solve nt conta mina tion. typic ally only a few barre ls of tars from clean ing of colum n are creat ed by thes e proc esse s. No waste sim~lar to the waste prev iousl y char acter ized exis ts. One manu factu rer desc ribes the recyc le strea m as follo ws: Benze ne 90-95 %; Glyco l 1-6%; other solve nts (cume ne, tolue ne) 1-4%. One of the manu factu rers inform ed us that he is using the waste for fuel in his boile rs and has been for the last ten years . Co-P rodu ct Wast e from Acet ic Acid Prod uctio n by N-Bu tane Oxid ation (Item 152). Five manu factu rers were surve yed. Only two respo nded to inform us that they have cease d produ ction . This was origi nally chara cteri zed as follo ws: water 0.1%; ash 5%; MED 1%; heati ng value of 9509 BTU/ lb; 101,7 00 MT/Y r. Cent rifug e and Dist illat ion Resid ues from Tolue ne Diiso cyana te Prod uctio n (Item 164). The origi nal repo rt descr ibes the waste strea m as follo ws: wate r 1%; ash 2%; Tolue ne Diam ine 0.001 %; 11,01 5 BTU/ lb; 107,9 00 MT/Y r. No infor matio n was given to confi rm or dispr ove this. Only two of the five produ cers surve yed respo nded. Both produ cers incin erate thei r wast es from this produ ct in order to steam . one of the produ cers gene rates about a ton per produ ce hour of waste . Deca nter Tar from Cokin g Oper ation s (Item 170). origi nal repo rt descr ibes the waste stream as follo ws: water The 0%; ash 20%; Naph thale ne 15%; 14,20 0 BTU/ lb; 39,80 0 MT/Y r. Eleve n coke produ cing facil ities respo nded to our surve y. Fifty -four lette rs were sent out; thre e were retur ned unde liver able and four respo nded that their facil ity no longe r produ ces coke.
-42-
Six of the seven facilities that did provide information indicated that they recycle their waste streams back to the coke oven. An analysis follows: Decanter tank tar sludge ·165,000 gals.
annual generation
current management practice entails recycling, by mixing this waste material with coal and charging to coke ovens. COMPOSITION: Naphthalene Phenol Solids ash content at 650°C BTU sulfur Chlorine
98% 0.060% 84.7% 27.5% l3, 820 BTU/lb 0.63% 0.18%
Total Metals Arsenic Barium Cadmium Chromium Copper Silver Zinc Lead Mercury Nickel Selenium
mg/1 0.8 <0.4 <0.03 <0.1 <0.1 <0.06 138.5 50.0 0.0120 <0.15 <0.003
l.
This analysis indicates very little naphthalene is present and 50% more ash is present. Other manufacturers that responded indicated up to 20% naphthalene and up to 0.5% phenol. Two facilities send their waste to landfill. Because of contamination of dirt, etc. one of the facilities sends 15% of the material to landfill. The other manufacturer sends all of the tar sludge to landfill. Summary Information was obtained on 14 of the 23 waste streams selected. We found that many of the waste stream descriptions that we obtained via survey were contradicting to the data available in literature.
-43-
All but two of the waste stream s we recei ved infor matio recy cled or destr oyed for bene ficia l use. In the n on were produ ction indus try there is t'he techn ology in pract ice plas tics haza rdou s wast e, but it is not share d betwe en produ to reduc e produ cers have exce llent treatm ent and other have none. cers. Some Resea rch is neede d for treatm ent of cyani de conta ining waste such as those resu ltant from prod uctio n of acry lonit rile. prec ipita tion proc esses could be used for recov ery. Perha ps waste s have been burne d; this meri ts more inves tigat ion. Cyan ide Rese arch is also neede d for treat ment of phen ol cont ainin g wast es. For exam ple, sele ctiv e adso rptio n with carb on. Liqu id/liq uid extra ction has been used in other pheno l conta ining waste s. '
-44-
SURVEY RESULTS, SUMf1ARY TABLE
Comments Obtained
Original Information
Item ~
Description
Energy Potential MM BTU/yr
No. of Inquires
No. of Responses
Yaste Description
Management
R&D
Practices ·
Required
All wastes associated with this process are recycled internally or recycled as feed to other products.
none
383
4
3
506
7
5
Polyethlybenzenes ·and Phenol Ethers and other miscellaneous high boilers. -18,500 BTU/lb -260oF open cup flash point could have 1-2% Halogen.
none All producers indicated that their waste streams were destroyed by incineration or in boilers. Two manufacturers sell this waste stream as blend oil and the others burn it in incinerators or boilers. One producer uses this stream as solvent and/or heat transfer fluid before incineration.
Ethylene Glycol/ Monobutyl ether production
140
9
2
60% Triethylene Glycol 25% Tetraethylene Glycol
sold
unknown
27
Adipic Acid from Cyclohexanol Oxidation
423
2
70
SIC 35 · Machinery 100
0
71
SIC 36 Electronics
177
0
73
SIC 2851 Paint & Allied Products
245
0
95
SIC 2833 Medicianls & Botanicals
71
0
79
SIC 2821 Plastic Material & Resins
118
8
92
SIC 2821 Plast'ic Products
105.3
16
11
SIC 2865
none
Dimethyl Tere-phthalate
from P·Xylene Oxidation
13
Ethyl benzene from Benzene Alkylation
14
,_I "'I
15% Sol ids
2
25·30% organic 1-112 - 2% Nitric Acid trace Cu, U and Monobasic acids
sold as S02 scrubbing chemical
none
6
Toluene with 10·30% Trichloro· ethylene; 10·20% Vinyl Chloride, Ethyl Chloride; 1-2% 200-300 tons/yr/facility
incineration
none
Phenol 4·5.5%; no ash; Formalde· hyde 0.1·0.25%; the rest is water. One producer has 0.1·0.2% resin. Another 1.5% methanol and some other organics 5·10 gpm/facility.
Varies ... direct to sewer with or without dilution. Total recycle. Phenol extraction. Incineration. Settling. Combinations of the above.
It appears that technology exists to handle this stream, but is not shared industry wide.
11
SURVEY RESULTS, SUMMARY TABLE (Continued) Original Information
c;orrments Obta'ined
Energy Item
I
Potentia t
No. of
MM BTU/yr
Inquires, Responses
No. of
~
Description
94
SIC 2869 K011, K013, K014
689.4
105
SIC 2867 Ethylene Production Quench 8 lowdown
685
108
SIC 2865 Phenol Production (aqueous wastes)
121
116
SIC 2879 Pesticide Production
107
0
117
SIC 2879 Pesticide Production
107
0
122
SIC 721 Spent Solvent
253
0
143
SIC 2865 403 Phenol Production Distillation Bottoms
10
3
151
SIC 2865 Benzene Production
101
34
11
152
SIC 2869 Acetic Acid Production
243
5
2
Toluene
299
5
2
+-
0' I
164
Di isocyanate
Production Centrifuge and Distillation
3
~aste
Management
R&D
Practices
Required
Deep well injection
Extraction into an organic stream and then incineration. Or concentration and recycle. Perhaps precipitate out.
varles ••. liquid/liquid extraction followed by recycle to crude unit; stripped before sewering; flocculation and skimming. Organics incinerated. ~ater used for boiler feed.
rnknown
direct to sewer
Extraction ard beneficial use of the phenol.
Phenol 5%; CLmYlph enol 40%; Alpha·Hethylstyrene Dimers 25%; Acetophenone 10%; other organics 20%.
Some recycle; boiler fuel
Possibly further research into recycling.
(recycle stream) 90·95% Benzene; 1·4% other solvents (cumene, toluene); 1·6% Glycol.
Total recycle or boiler fuel.
none
1 ton/hr/facility no description provided.
incineration
none
Description
<1000 ppm CN aqueous
K011: organic 11,000 ppm roc 108,000 mg/l o.s. 260 mg/l s.s. K013: organic 6,000 mg/l 13
3
-1% organic; 98% water, some metals
500·1000 ppm phenol;
-so
gpm
1
SURVEY RESULTS, SUMMARY TABLE (Continued) Original Information Item
I
+"-.] I
Comments Obtained Energy Potential MM BTU/yr
~
Description
168
SIC 2869 Linear 128 Alkyl Benzene Sulfonate Production
170
SIC 3312 Coking Operations decanter Tar
142
No. of Inquires
No. of Responses
~aste
Description
Manageolent ·Practices
2·20% Naphthalene; 0.06·0.5% Phenol; 20·30% ash; up to 4% inorganic salts.
Total recycle to coking oven in most cases, but some still goes to landfill.
R&D
Regui red
0
54
4
Improvement of recycle.
REFERENCES 1.
Weinstein, N. J. waste Oil recycling and Disposal. 670/2-74-052 , August 1974, 344 pp.
2.
Brinkman, D. W. et al. Environmenta l, Resource Conservation , and Economic Aspects of Used Oil Recycling. DOE/BETC/RI80/ll, April 1981, 59 pp.
3.
Cotton, F. 0. Waste Lubricating Oil: An Annotated Review. 1982 Revision, DOE/BETC/IC -82-4, October 1982. 272 pp.
4.
Citations from the NTIS Data Base. Waste Oil Reclamation (1964-June 81), PB81-807471. NTIS. 62 pp.
5.
citations from the NTIS Data Base. Organic Solvent Recovery and Reclamation (June 70-June 83). PB83-86748l. NTIS. 259 pp.
6.
Citations from the Engineering Index Data Base. Organic Solvent Recovery and Reclamation (June 70-June 83). PB8386753. NTIS. 104 pp.
7.
Industrial Waste Exchanges. 1982', p. 33.
8.
40 CFR Parts 260-271.
9.
Kincannon, B. Oily Waste Disposal by Soil Cultivation Process. EPA-R2-72-ll 0, December 1972, 116 pp.
10.
Knowlton, A. E. An Overview of Resource Recovery in Petroleum refineries. Industrial Wastes, November/Dec ember 1983, p. 8-10.
11.
Engineering- Science, Inc. The 1976 API Refinery Solid Waste Survey. American Petroleum Institute, March 1978.
12.
Coke and Coal Chemicals. Minerals Yearbook. U.s. the Interior, 1976.
13.
Lowry, H. H., Ed. Chemistry of Coal Utilization, Vol. II. National Research Council, 1945. p. 1297-1300.
14.
Galliker, J. P. Energy Price and Expenditure Data Report, 1970-1980. DOE/EIA-0376 , July 1983, 282 pp.
15.
Brenner, 11-14.
H. R.
Pollution Engineering. January
Coproduct Utilization, CEP,
-48-
EPA-
Dec.
Dept.
of
1983, p.
16.
Micallef, R. A. and A. T. B. P. Squires. Reclamation of Synthetic Turbine Engine Lubricants. AFWAL-TR-81-2072, Wright Patterson Air Force Base, August 1981, 105 pp.
17.
Maple, R. E. and A. R. Price. Waste Chemicals Have Value .... sometimes. Hydrocarbon Processing, October 1972, p.l68-172.
18.
Hatch, L. and s. Matar. From Hydrocarbons to Petrochemicals Hydrocarbon Processing, Part 9. Production of Olefins, March 1978, p. 129-139; Part 5, Non-Hydrocarbon Chemicals from refinery Streams, September 1977, p. 165-173.
19.
Schuetze, B. and H. Hofmann. How to Upgrade Heavy Feeds. Hydrocarbon Processing, February 1984, p. 75-82.
20.
Lauber, J. D. Burning Chemical Wastes as Fuels in Cement Kilns. Journ. of the Air Pollution Control Association ~' No. 7, July 1982, p. 771-778.
21.
Private communication from U.S. EPA Office of Solid Waste.
22.
Beggs, T. w. and v. M. Patankar. Accelerated Baghouse Corrosion in a Waste Oil Burning Asphalt Concrete Plant. Presented to 72nd Ann. Meet. Air Pollution Control Assoc., Cincinnati, OH, June 24-29, 1979.
23.
Andrews, G. F. and R. Trapasso. Risks Associated With Waste-Fuel Use In Cement Kilns. Environmental Progress dt No. 1, February 1984, p. 64-70.
24.
Guidance Manual for Hazardous·waste Incinerator Permits. PB84-100577, NTIS, 1983, 128 pp.
25.
Recon Systems, Inc. and ETA Engineering, Inc. Burned As A Fuel. SW-892, U.S. EPA, 1980, 213 pp.
26.
Reynolds, Smith and Hills. An Assessment of the Technical and Economic Feasibility of the Conversion of Hazardous Industrial Waste Into Energy. Contract No. 68-01-3569, u.s. EPA, September 1977, 307 pp.
27.
Haggin, J. and J. Krieger. in U.S. Energy Mix. Chem. 28-30.
28.
Suarez, M. Acid Sludge Utilization. September 1980, 31 pp.
-49-
Used Oil
Biomass Becoming More Important & Eng. News, March 14, 1983, p. DOE/BC/1009-1,
29.
Becke r, K. P. Fluid Bed Incin eratio n of Waste s. Progr ., Octob er 1976, p. 61-68.
30.
Daven port, c. H. 144.
31.
Shold rick, M. G. Ethyl ene from Heavy Feeds tocks. Eng., Augus t 15, 1966, p. 122-12 4.
32.
Cusak , J. and R. H. Mashf ord. Pasca l Makes Ethyle ne from Resid . Hygr. Proc., Janua ry 1974, p. 127-12 9.
33.
Hosoi , T. and H. G. Keist er. Ethyle ne from Crude Oil. Chern. Eng. Progr . 71, No. 11, Novem ber 1975, p. 63-68.
34.
Gree k, B. F. Natio nal Gas Liqu ids Rema in stron g Petroc hemic al Feeds tock. Chern. & Eng. News, March 12, 1984, p. 17-38 .
35.
Nagle r, B. Dispo sal of Metal worki ng Fluid s. Tooli ng Produ ction, Febru ary 1983, p. 59-64 .
36.
Gabr is, T. Emu lsifie d Indu stria l DOE/B C/1018 3-1, April 1982, 142 pp.
3 7.
Yates , J. J. et al. An Inven tory of Used and By-Pr oduct Hydro carbon Stream s, EPA-6 00/7-8 2-031, May 1982, 110 pp.
38.
Natio nal Air Pollu tant Emiss ion Estim ates, 1940-1 976. EPA450/1-78~002, July 1978, 33 pp.
39.
Wein stein, K. D. et al. Enhan ced Utili zatio n of Used Lubri cating Oil Recyc ling Proce ss By-Pr oducts . DOE;B C/1005 919, March 1982, 157 pp.
40.
Harris on, J. W. et al. Assess ment of Hazard Poten tial from Comb ustion of Waste s in Indus trial Boile rs. EPA-6 00/S7- 81108, Augus t 1981.
41.
Bonne r, T. et al. Hazar dous Waste Incin erato r Engin eering . Noyes Data Corp. , Park Ridge , NJ, 1981, 432 pp.
42.
Priva te comm unica tion from E. Timot hy Oppe lt, Chief Incin erati on Resea rch Group , Energ y Pollu tion Contr ol, Divis ion, EPA Indus trial Enviro nment al Resea rch Labor atory, cincin nati, Ohio.
43.
Wein stein, N. J. Unco nvent ional Fuels . Handb ook of Air Pollu tion Techn ology, John Wiley & Sons, March 30, 1984.
Ethyle ne.
-50-
Chern. Eng.
Petr. Ref., March 1960, p. 125-
Oils
Chern.
&
Recy cling .
44.
Subdew Condensing Heat Exchangers. TR-83-900165 , Andersen 2000, Peachtree City, GA, March 30, 1983, 15 pp.
45.
control of Volatile Organic Emissions from Existing Stationary Sources. Vol. I: Control Methods from Surface Coating Operations, EPA-450/2-76 -028, Nov. 1976. Vol. II: Surface Coating of Cans, Coals, Paper, Fabrics, Automobiles, and Light Duty Trucks, EPA-450/2-77 -008, May 1977. Vol. III: surface coating of Metal Furniture, Dec. 1977. Vol. IV: Surface Coating for Insulation of Magnet Wire, EPA-450/2-77 033, Dec. 1977. Vol. V: Surface Coating of Large Appliances, EPA-450/2-7 7-034, Dec. 1977. Vol. VI: surface Coating of Miscellaneo us Metal Parts and Products, EPA-450/2-78 -0.15, June 1978. Vol. VII: Factory Surface Coating of Flat wood Paneling, EPA-450/2-78 -032, June 1978.
-51-
APPENDIX A ~ASTE
ITEM 1
INFO. SOURCE A
TYPE OF WASTE NONAQ. LIQUID/ AQUEOUS SOLID X
HYDROCARBON COMPILATION
TYPE OF INDUSTRY/ EROCESS Acetone
SOURCE OF WASTE
from Isopropanol
Acetone Sludge
Crude
INDUS. TOTALS ~ MT/Yr
Dehydrogenation
2
A
Liquid
Acetone Prod.
Light Ends
1725 MT/Yr
~ASTE
CHARAC./COMMENTS Isopropanol 6% Acetone 59% Yater 33% Other 2% HV=8297(*) THV=1.3 Propylene 17% Organic 18%
Acetone 65% HV=1345D(*) THV=5.8 3
A
4
A
5
A
X
Acetylene Prod.
Acetylene 2633 Recovery MT/Yr
Kerosene 21% Yater 79% HV=3780(*) THV=2.5
Liquid
Chloroprene Prod.
J,Jaste Organics
18614 MT/Yr
Polymers 42.9% Catalyst 14.2% High Boilers 42.9% HV=12870(*) THV=60.3
Liquid
Crude Tere·
Xylene Recovery
545 MT/Yr
M·xylene 45% O·xylene 45% Other 10% HV=16200(*) THV=2.2
Drain on
1367 MT/Yr
Yater 75% Isobutane 13% Propane 11.5% Other 0.5% HV=4500(*) THV=1.5
143 MT/Yr
Diisopropyl Benzene 66% Butyl Benzene 28% Other 6% HV=14722(*) THV=0.53
Waste Solvent
17252 MT/Yr
Toluene 50% Xylene 35% Other 15% HV=16379(*) THV=71.2
phthalic
Acid Prod.
6
7
A
A
X
Liquid
Cumene from Benzene
Accumu·
Alkylation
La tor
Cumene Prod.
0 i st i l· Lation Bot toms
8
A
Liquid
Cyanuric Chloride
from HCN Chlorination 9
A
Liquid
SIC 2869 Cyclohexanol from Phenol Hydrogenation
Light Ends
2724 MT/Yr
Benzene 45% Cyclohexane 45% Other 10% HV=17717(*) THV=12
10
A
Liquid
SIC 2865 Cyclohexanol Prod.
Heavy Ends
5630 MT/Yr
Cyclohexanol 32% Phenol 9% Heavy Ends 59% HV=13336(*) THV=18.9
11
A
Liquid
SIC 2865 Combined Dimethyl Tere· \.laste phthalate from P·Xylene Oxidation
13620 MT/Yr
Methyl P·formyl Benzoate 83% Methyl Hydrogen Terephthalate 9% Other 8% HV=11165(*) THV=383
A-1
W'ASTE HYDROCARBON COMPtLATJON (continued) TYPE OF ITEM 12
INFO. SOURCE A
AQUEOUS
~ASTE
NONAQ. LIQUID/ SOLI 0 liquid
TYPE OF INDUSTRY/ PROCESS Ethanolamines from Ethylene Oxide
SOURCE OF ~ASTE
Triethanolamine Column
INDUS. TOTALS i;72"2 MT /Y r
~ASTE
CHARAC.[COMMENTS Triethanolamine SO% Heavy Ends SO% HV=11814(*) THV=14.1
13
A
Liquid
Ethyl benzene from Benzene Alkylation
Heavy Ends
136200 MT /Yr
Diethylbenzene 59% Polyethylbenzene 11% S-Butylbenzene 10% Aluminum Chloride 18% Other 2% HV=14760(*) THV=506
14
A
Liquid
Ethylene Glycol Monobutyl Ether Prod.
Triethylene Glycol Column
53118 MT/Yr
Heavy Ends 98% Triethylene Glycol 2% HV= 11944(*) THV=160
15
A
Liquid
Ethylene Glycol Monobutyl Ether Prod.
Heavy Ends
3269 MT/Yr
Heavy Ends 76% Sodium Butylate 18% Triethytene Glycol Butyl Ether 6% HV=1290D(*) THV=10.6
16
A
Liquid
Ethylene Glycol Monobutyl Ether Prod.
Heavy Ends
5811 MT/Yr
Heavy Ends 84% Triethylene GlyCol Butyl Ether 4% Other 12% HV=13680(*) THV=20
17
A
Liquid
Hexamethylene Diamine Prod.
Liquid Organics
5811 MT/Yr
Cyclohexane 20% Adipic Acid 20% Hydroxycaproic Acid 20% 1,6·Hexanediol 20% Other 20% HV=12435(*) THV=18.2
18
A
Liquid
Hexamethylene Diamine from Hydrogenation of Adiponitrile
272 MT/Yr
Heavy Ends/Tars 100% HV=18000(*) THV=1. 2
19
A
Liquid
Methyl Isobutyl Ketone Prod.
Heavy Ends
5176 MT/Yr
Phorones 42% Mesitylene 55% Mesityl Oxide 3% HV=15937(*) THV=21
20
A
Resorcinol Propylene Oxide Prod.
Scrubber Waste
19068 MT/Yr
Water 48% Chlorohydrins 34% Chlorine 15% Other 3% HV=1700(*) THV=8.2
21
A
Liquid
Styrene from Oehydrogena · tion of Ethyl Benzene
Heavy Ends
1816 MT /Yr
Styrene Monomer 20% Styrene Trimer 20% Stilbene 20% Phenathrene 20% Other 20% HV=18000(*) THV=8.2
22
A
Liquid
Toluene Diisocyanate Prod.
TDA Light Removal
7082 MT/Yr
0-Toluenediamine 100% HV=14845(*) THV=26.5
X
A-2
I
WASTE HYDROCARBON COMPILATION (continued) TYPE OF ITEM
~
INFO. SOURCE A
24
A
25
A
26
A
27
A
28
A
29
AQUEOUS
~ASTE
NONAQ, LIQUID/ SOLID Liquid
X
TYPE OF INDUSTRY/ PROCESS Trichloro· ethylene and Perchloro· ethylene Prod.
SOURCE OF WASTE Heavy Ends
INDUS. TOTALS 27240 MT /Y r
~ASTE
CHARAC.[COMMENTS Hexachlorobutadiene 34% 1, 1, 1-Trichloroethane 5% 1,1,2,2-Tetrachloroethane 23% Hexachlorobenzene 20% Other 18% HV=2699(*) THV=18.5
Trichloro· Waste ethylene and \.Jater Perchloroethylene Prod.
143 MT/Yr
Water 75% Phosgene 25% HV=223(*) THV=0.008
Liquid
Trichloro· ethylene and Perchloro· ethylene Prod.
962 MT /Yr
Carbon Tetrachloride 92.6% Trichloroethylene 7% Other 0.4% HV=619(*) THV=0.15
Liquid
Trichloro· Heavy ethylene and Ends Perchloro· ethylene from Oxychlorination
2996 MT/Yr
Hexachlorobutadiene 25% Hexachlorobenzene 30% Hexachloroethane 10% Other 35% HV=2723(*) THV=2.1
Adipic Acid from Cyclo· hexanol Oxidation
!,,aste Oil Stream
742744 MT/Yr
Succinic Acid 11% Glutaric Acid 11% Adipic Acid 11% \.later 67% HV=2263(*) THV=423
liquid
Benzoic Acid from Toluene Oxidation
Centrifuge 1271 Effluent MT/Yr
2·Methyl 0 i phenyl 26% 3·Methyl Diphenyl 19% Benzyl Benzoate 29% Diphenyl 10% Other 16% HV=13919(*) THV=4.5
A
Liquid
Caprolactam from Cycl o· hexanone
Purifica· 8172 tion MT/Yr Residues
Tars 100% HV=18000(*) THV=37.1
30
A
Liquid
Chlorinated Methanes from Methanol
Heavy Ends
908 MT /Yr
31
A
liquid
Dimethyl Light Terephthalate Ends from Esterifi· cation of TPA
13620 MT/Yr
Dimethyl Ether 32% Dimethyl Terephthalate 63% Methyl P·Formyl Benzoate 5% HV=10701(*) THV=36.7
32
A
Liquid
Ethyl Acetate Low from Ethanol Boilers Esterification (Ethyl Acetate)
1362 MT/Yr
Low Boilers 100% HV=10432(*) THV=3.6
33
A
Liquid
Ethyl Esterifi· 2906 Acrylate Prod. cation MT /Yr Heavy Ends
X
Carbon Tetra· chloride Removal Effluent
A-3
Carbon Tetrachloride 63% Trichloroethylene 4% 1,1,2-Trichloroethane 5% Chloroform 18% .Other 10% HV=819(*) THV•0.2
Ethyl Acetate 49% High Boilers sa HV=11232(*) THV=8.2
~ASTE
ITEM 34
35
36
INFO. SOURCE
TYPE OF YASTE NONAO. LIOUIO/ AQUEOUS SOLID Liquid
A
Liquid
A
Liquid
A
HYDROCARBON COMPILATION (continued)
TYPE OF INDUSTRY/ PROCESS Ethyl Glycol Monomethyl Ether Prod.
SOURCE OF YASTE
Glycerin
from Propylene
Heavy Ends· Allyl
Oxide
Alcohol
Glycerin from Propylene Oxide
Light Ends· Allyl
Heavy Ends
INDUS. TOTALS 5630
CHARAC./COMMENTS Triethylene Glycol
MT /Y r
Methyl Ether 3%
from Triglycol Ether Column
Heavy Ends 86% Sodium Methylate 11% HV=10680(*) THV=15.1 136 MT/Yr
Allyl Alcohol 99.7% Other 0.3% HV=13924(*) THV=0.5
908 MT/Yr
Propylene Oxide 14.7% Allyl Alcohol 18.7% Acetone 21.8% Propionaldehyde 44.8% HV=12892(*) THV=2.9
318 MT/Yr
Diisobutyl Ketone 50% Heavy Impurities SO% HV=14248(*) THV=1.1
1634 MT/Yr
Peracetic Acid 11% Light Impurities 68% Allyl Alcohol 15% Other 6% HV=6168(*) THV=2.6
726 MT/Yr
Heavy Impurities 84% Glycerin 5% Yater 6% Other SX HV=10080(*) THV=1.8
Light
454
Ends·
MT/Yr
Tars 60% Terphenyls 29% Other 11X HV=18750(*) THV=2.1
Alcohol
37
Liquid
A
Glycerin from Propylene Oxide
Light
Ends· Glycidol
Section
38
39
40
A
Liquid
liquid
A
Liquid
A
Glycerin from Propylene Oxide
Glycerin from Propylene Oxide
Glycerin Prod.
Light
Ends· Glycidol
Heavy
Ends· Glycerin
Glycerin
41
liquid
A
Hexamethylene Diamine Prod.
HMDA Spent
272 MT/Yr
Organics 30X Spent Catalyst 70% HV=3600(*) THV=0.3
454 MT /Yr
Oil 100X HV=18000(*) THV=2.1
Catalyst
42
Liquid
A
43
A
44
A
45
A
Hexamethylene Diamine Prod,
~ASTE
~aste
Oil
Hexamethylene Diamine Prod.
Yaste By· Products
999 MT/Yr
Organic Amines 50% Organic Imines 50% HV=13695(*) THV=3.4
X
Isoprene Prod.
Amylene Recovery Column
20884 MT/Yr
Water 90% N·Hexane 10% HV=1800(*) THV=9.5
X
Maleic Anhydride from N·Butane Oxidation
Combined Waste
6084 MT/YR
Organic Acids 49% Yater 51% HV=5880 THV=9
Liquid
A-4
~ASTE
ITEM
46
INFO. SOURCE
TYPE OF WASTE NONAQ. LIQUID/ AQUEOUS SOLID
A
Liquid
HYDROCARBON COMPILATION (continued)
TYPE OF INDUSTRY/ PROCESS
SOURCE OF WASTE
N·Butyl
'Esteri·
Acrylate Prod. fication
47
A
Liquid
Total Recycle
INDUS. TOTALS
1;358 MT/Yr
MEA Waste 9080
from Urea
MT /Yr
Production 48
A
Liquid
Total Recycle
Waste OiL 9080
from Urea
MT /Yr
Production 49
A
Liquid
Vinyl
Ethyl Acetate
Acetate
·Prod.
50
B
Liquid
still Bottoms
B
liquid
Acetonitrile Prod.
Crude Aceto·
5900 MT/Yr
Acetonitrile 25% Acrolein, Acrylamide, etc. 75% HV=7000·7500 THV=10.4·11.2
· 6615 MT /Yr
nitrile
Bottoms (KD13) 52
B
X
53
B
Sludge
Lube Oils 80% Yater 20% HV=144DO(*) THV=33 Acetic Acid 9% Vinyl Acetate 45% Ethyl Acetate 46% HV=9983(*) THV=6.8
Prod,
51
Degraded MEA 1DO% HV=120DO(*) THV=27.4
2724 MT/Yr
Bottoms
SIC 2869 Acrylonitrile
YASTE CHARAC./COMMENTS Ethyl Acetate 49% High Boilers 51% HV=11232(*) THV=12.3
SIC 28694 Phorate Prod.
Waste Water IK038)
Chlordane Prod.
1./aste
13600
\Jater
MT/Yr
Acetic Acid, Succinonitrile , Hydrocyanic Acid, etc. HV=10000(*) THV=16.7 Phorate, Formaldehyde, Phosphorothioc Acid Esters, etc. HV=5000·6000
Treatment sLudge
Hexachlorocyc lopentadiene, Other Chlorinated Compounds, HV=3000·40DD THV=10.7·14.3
(032) 54
B
sLudge
SIC 28694
Phorate Prod •.
55
B
Liquid
SIC 28694 2,4,5-Tri· ch l oi'oph enoxy
'Waste \.Jater' Treatment Sludge (K04D)
Phorate, Formaldehyde, Phosphorothioc Acid Esters, etc.
Heavy Ends (K042)
Chlorinated Benzene, Chlorinated Organic, etc. HV=50D0·7000
Acetic Acid Prod. 56
B
Liquid
SIC 2869 2,6·Dichloro· 2,4-Dichloro· phenol phenoxy Acetic
Acid Prod. 57
B
58
B
Sludge
X
Chlorophenol Polymers, 2,4·Dichloroph enol, 2,6·Dichloroph enol
SIC 2892 Explosive Prod.
Yaste 1000 \.Jater MT/Yr Treatment Sludge
Nitrocellulose 75% Other 25% HV=7DOO THV=1.8
Degreasing Operation
Halogen· 99000 ated MT/Yr Hydrocarbon Solvents
Trichloroethyl ene, Perchloro· ethylene, Methylene Chloride, etc. HV=3000 THV=74.8
A- 5
WASTE HYDROCARBON COMPILATlON (continued)
TYPE Of INFO. SOURCE B
AQUEOUS
~ASTE
HOHAQ. LIQUID/ SOL! D
TYPE Of INDUSTRY/ PROCESS
SOURCE Of ~ASTE
Various
X
Halogenated Organic Solvents (f002)
Operations
60
61
B
B
Liquid
Liquid
IHOUS. TOTALS
Solvents
SIC 2251
Solvents
360 MT/Yr
Benzene, Xylene, Perchloroethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.19·1.7
Solvents
740 MT/Yr
Benzene, Xylene, Perchloro· ethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.39·3.45
130
Benzene, Xylene, Perchloro· ethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.07·0.6
15 MT /Y r
Production B
Liquid
SIC 2261
Cotton Finishing Plants
63
B
Liquid
SIC 2269
Solvents
Textile Finishing Plants
64
B
Liquid
MT/Yr
SIC 2272
B
Liquid
SIC 2291 Felt Goods
200 MT/Yr
Renzene, Xylene, Perchloro· ethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.11·0.93
Solvents
3 MT/Yr
Benzene, Xylene, Perc~loro· ethylene, Trichloroethylene HV•2000 ·18000 THV•0.002·0.07
Solvents
30 MT/Yr
Benzene, Xylene, Perchtoro· ethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.016·0.14
Solvents
20 MT/Yr
Benzene, Xylene, Perchloro· ethylene, Trichloroethylene, etc. HV•2000·18000 THV•0.011·0.09
Solvents
4600
Naphthas, Toluene, Xylene, Ethyl Alcohol, Amyl Alcohol HV•14000 THV•16.7
Production
66
B
Liquid
SIC 2297
Nonwoven Fabrics 67
B
liquid
SIC 2299 Textile
Goods 68
B
Liquid
SIC 25·
Benzene, Xylene, Perchloro· ethylene, Trichloroethylene, etc. HV•2000 ·18000 THV•0.008·0.07
Solvents
Tufted Carpets and Rugs Production 65
CHARAC./COMMENTS Tetrachloroethylene, Methylene Chloride, Trichloroethylene, etc. HV•220D
SIC 2231 \.Joel Weaving and Finishing Mill
\Jomen•s Hosiery
62
~ASTE
Furniture and
MT/Yr
Fixtures
69
B
Liquid
SIC 2841 Solvents Soap and Detergent Prod.
16300 MT/Yr
Alkyl Benzene, Alcohol, Ethoxylates HV•14000 THV•55.3
70
B
Liquid
SIC 35· Machinery
Halogen· ated and Nonhalogenated Solvents
99414 MT/Yr
HV•4000 THV•1000
71
B
Liquid
SIC 36· Electronic
Halogen· ated and Nonhalo· gena ted Solvents
175827
HV•4000 THV•177
SIC 2851 Paint and Allied Prod.
Spills and Spoiled Catches
72
B
Liquid
A-6
MT/Yr
11898 HT/Yr
Phenol, Toluene, Benzene, Trichloroethylene, etc. HV•13000(*) THV•39
YASTE HYDROCARBON COMPILATION (continued)
ITEM
n--
INFO. SOURCE
TYPE OF WASTE NONAO. LIOUID/ AQUEOUS SOLID
B
Liquid
TYPE OF INDUSTRY/ PROCESS SIC 2851
SOURCE OF WASTE Solvents
Paint and Allied Prod.
74
B
Liquid
liquid
B
WASTE CHARAC./COMMENTS Solvents 53·85% Pigments, Resins 15·45% Inorganic Residue 0·2% HV=14000 THV=247
Acetonitril e, Chloroform, Ethylene Dichloride, etc. HV=2500 THV=4. 5
SIC 2833
Halogen·
7056
Medicinals
ated
MT/Yr
Nonhalo·
81325 MT/Yr
Acetone, Benzene, Amyl Acetate, Ethanol, etc. HV=13000 THV=266
and Botanicals Yaste Solvents 75
INDUS. TOTALS 70004 MT/Yr
SIC 2833
Medicinals genated and Botanicals Waste Solvents
76
B
Liquid
SIC 2833 Organic Medicinals Waste and Botanicals Residue
28224 MT/Yr
Tars, Still Bottoms, Sludges HV=10D00 THV=71
77
B
Liquid
SIC 2833 Wastes Medicinals and Botanicals
3528 MT/Yr
Activated Carbon, Filter Aid, Heavy Metals, Flammable Solvents, etc. HV=3000 THV=2.7
78
B
SIC 2831 Biological
Process Waste
722 MT /Y r
Ethanol 40% Water 58% Other 2% HV=4600 THV=0.8
SIC 2821
St it l
Plastic
Bottoms
29204 MT /Y r
Heptane, Xylene, Cyclohexane , Propylene, etc. HV=16000 THV=118
Still Bottoms
20341 MT/Yr
Styrene, Butadiene, Hydrocarbon Solvent, etc. HV=160DO THV=82
1634 MT/Yr
Hexachloroe thane 48% Tetrachloro ethylene 52% HV=2000 THV=0.82
X
Prod.
79
B
Liquid
Materials and Resins 80
B
Liquid
SIC 2822 Synthetic
Rubber 81
82
A,B
c
liquid
X
Rubber Plant
Waste 'Water
Carbon Black Oil Latex, Rubber
X
Steel
'Waste Water
Oil 1X Suspended Sol ids
( 1)
83
c (2)
84
c
Industry X
Fish Plant
Plant Effluent
X
Poultry
Process 'Waste
Water 60% Oil/Grease 20%
Steel Industry
Hydraulic System
\.later, Solids, Hydraulic Fluid
Paper Industry
Pulping Processing
Acetic Acid 0.5·5%
Transportat ion 'Wastes
'Water 60·80% Free Oil 20·40%
( 3)
85
c ( 4)
86
c
Liquid
(5)
87
c
X
(6)
88
c (7)
Carbon Tetra· Heavy chloride Prod. Ends
sludge
A-7
14000 MT/Yr
Crude Protein, Crude Oil, Suspended Solids HV=5000(*) THV=17.6
WASTE HYDROCARBON COMPILATION (continued)
ITEM
~
INFO. SOURCE
c
TYPE OF WASTE NONAQ. LIQUID/ AQUEOUS illlQ X
(8)
90
0
TYPE OF INDUSTRY/ PROCESS Motor
SOURCE OF WASTE
'Waste \Jater
Sludge
SIC 2491
\Jaste
\Jood Pre·
Water
serving Process 0
Sludge
2.01.02
92
0
YASTE CHARAC./COMMENTS Oil, Zinc, Suspended Solids
Industry
2.01. 01
91
INDUS. TOTALS
SIC 2821
53000 MT/Yr
Plastics Prod.
X
2.01.03
15400 MT/Yr
Yater 90%
Ash 5% Pentachlorophenol 0.08% HV=645 THV=2.5 \.later
75%
Phenol 5%
Ash 20% HV=861 THV=11.5
SIC 2821
486000 MT/Yr
Plastics Prod.
Water 91% Ash 2% Phenol 5%
Formaldehyde 2%
HV=861 THV=105.3 93
0
X
2.02.01
SIC 2869 Acetaldehyde Production from
399500 MT/Yr
Ethylene
Oxidation
94
0
X
2.02.02
SIC 2869 K0,-1, K013 and K014 Prod.
3181000 MT/Yr
Water 97% Ash 2% Chloroform 0.3% Formaldehyde 2% HV=170 THV=17.1
Yater 98% Ash 2% Acryloni·tri Le 0.04% Cyanide 0.3% Acetonitrile 0.6%
HV=861 THV=689.4 95
0
X
2.02.03
SIC 2869 Fluorocarbon
270 MT/Yr
\Jater 95% Antimony 0.2% Chloroform 0.04% Carbon Tetrachloride 0.04% Other 4X HV=O THV=O
39950
\.later 98% Nitrobenzene 0.35% Benzene 0.5% Aniline 0.01% Other 1%
Prod.
96
0
X
2.02.04
SIC 2865 Aniline
\Jaste \Jater
MT /Yr
Prod.
HV=258 THV=2.6 97
0
X
2.02.05
SIC 2865 Chlorobenzene
Process \Jaste
520 MT/Yr
Prod.
'Water 99.7% Benzene 0.18% Chlorobenzenes 0.018%
HV=43 THV=0.006 98
0
2.02.06
X
SIC 2869 Methyl Ethyl
1440 MT/Yr
\.later 50%
Ash 2% Paraldehyde 36.5% Pyridine 3% 2·Piccoline 3%
Pyridine Prod.
HV=8606 THV=3.1
A-8
~ASTE
TYPE Of l~fO.
ITEM 99
~ D
AQUEOUS X
2.02.07
100
101
0 2.02.08
D 2.02.09
X
X
HYDROCARBON COMPILATION (continued)
~ASTE ~O~AQ.
TYPE Of
LIQUID/ SOLID
I~DUSTRY/
SOURCE Of
I~DUS.
~ASTE
PROCESS SIC 2869 Glycerin Prod· uction from Allyl Chloride
~ASTE
TOTALS 2100 MT/Yr
CHARAC.LCOMMENTS \.later 92% Ash 2X Toluene 5% HV=1076 THV=0.57
SIC 2865 Maleic Anhydride Prod.
Vent Scrubber
90800 MT/Yr
\.later 83% Ash 2% Benzene 16.7% Maleic Anhydride 0.1% HV=2926 THV=66.9
172500 MT/Yr
\.later 50% Ash 2% 1,2·Dichloroethane 21.9% Methyl Chloride 2.1% Vinyl Chloride 2.5%
Effluent
SIC 2869
\.Jaste
Ethylene Dichloride
\.later
Prod.
Chloroform 0. 1%
Carbon Tetrachloride 0.1% Other 21% HV=2125 THV=93.4 102
D 2.02 .1 0
X
SIC 2865
Spray
Phthalic Anhydride by
Scrubber , MT /Yr
30000
Effluent
Naphthalene Process 103
0 2.02.11
X
SIC 2865 Methylene Di phenyl
Phthalic Anhydride. 0.1%
HV=620 THV=4.7
Amine Recovery
187000 MT/Yr
Heavy Ends
15500 MT/Yr
Di isocyanate
Prod. 104
0 2.02.12
X
SIC 2869 Ethylene
Water 89% Ash 2% Maleic Anhydride 10%
Oxide Prod.
\.later 95%
Ash 2% Aniline 5% HV=818 THV=38.5 \.later 65% Ash 2% Acetaldehyde 16%
Other 17%
HV=4303 THV=16.9 105
106
D 2.02.13
0
X
S1C 2869 Ethylene Prod.
Quench
Slowdown
8172000 MT/Yr
Yater 98% Toluene 0.2% Phenol 0.04% Benzene O.BX Other 1% HV=333 THV=685
X
SIC 2869 Ethylene Prod.
Quench Slowdown
5448000· MT/Yr
'Water 98% Toluene 0.4% Phenol 0.3% Benzene 0.5% HV=344 THV=472
2. 02.14
107
0 2.02.15
X
SIC 2869 Methyl Methacrylate Prod.
Quench Tower
1398300 MT /Yr
'Water 30% Methyl Methacrylate 0.3% Other 69.7% HV=231 THV=81.3
108
D 2. 02. 16
X
SIC 2865 Phenol Prod.
Decanter I.Jastes
1398000 MT/Yr
\.later 92% Phenol 2% Other 6% HV=344 THV=121
A-9
~ASTE
TYPE OF l~FO.
~ASTE ~O~AO.
TYPE OF
l!OU!O/
l~OUSTRY/
~
PROCESS SIC 2869 Ethylene Oxide Prod.
SOURCE OF 1,./ASTE Cooling Tower
TOTALS 291500 MT/Yr
l~OUS.
YASTE CHARAC.LCOMMENTS \.later 99% Ethylene Oxide 1% HV=172 THV=12.6
ITEM 109
SOURCE 0 2. 02.17
110
0 2.02.18
X
SIC 2865 Dimethyl Terephthalate Prod.
\.laste \.later
136200 MT/Yr
!,.later 93% Formaldehyde 1.4% Other 5,6% HV=430 THV=14.7
111
0 2.02.19
X
SIC 2865 \.laste Bi sphenol 'Water Production by Acetone Phenol Process
118000 MT/Yr
Water 98% Phenol 1% Other 1% HV=280 THV=8.3
112
0 2.02.21
X
SIC 2865 Phenol Prod.
Aceto· phenone
12500 MT/Yr
\.later 70% Phenol 1% Other 29% HV=129 THV=0.41
113
0 2.02.22
X
SIC 2869 Methyl Ethyl Ketone Prod.
'Waste 'Water
3630 MT/Yr
Water 71% Methyl Ethyl Ketone 0.3% Other 28.7% HV=430 THV=0.39
114
0 2.02.23
X
SIC 2869 Glycerin Prod.
115
0 2.03.01
X
SIC 2879 Toxaphene Prod.
\./aste
SIC 2879 Pesticide Prod.
\.laste
116
0 2.03.90
AQUEOUS
HYDROCARBON COMPILATION (continued)
X
X
Azeotrope 2720 -Decanter MT/Yr Effluent
~ai:er
5000 MT /Yr
\.later 75% Toxaphene 1% Other 24% HV=4303 THV=5.4
500000 MT/Yr
'Water 75% Ash ZO% Parathion 3% Other 2% HV=850 THV=107
Treatment Sludge
~ater
'Water 64% Methyl Ethyl Ketone 2% Other 34% HV=293 THV=0.2
Treatment Sludge
117
0 2.03.91
X
SIC 2879 Pesticide Prod.
\.laste 500000 \.later MT/Yr Treatment Sludge
Yater 75% Ash 20% Chlorodane 3% Other 2% HV=850 THV=107
118
0 2.04.01
X
SIC 2491 \Jood Pre· serving Process
1,./aste 35700 Yater MT /Yr Treatment Sludge
\.later 90% Ash 5% Acenaphthene 0.03% Chrysene 0.01% Fluorene 0.03% Other 5% HV=5164 THV=46.4
119
0 3. 01.01
Spent Solvent
Water 0% Ash 2% Trichloroethylene 80% Other 18% HV=17212 THV=78
Liquid
A-10
18000 MT/Yr
\.JASTE HYDROCARBON COMPILATION (continued)
ITEM 120
INFO. SOURCE D 3. 01.02
TYPE OF WASTE NONAQ. LIQUID/ AQUEOUS SOLID liquid
TYPE OF INDUSTRY/ PROCESS
SOURCE OF WASTE Spent Solvent
INDUS. TOTALS 16000 MT/Yr
WASTE CHARAC./COMMENTS \.Jater 0% Ash 2% 1, 1, 1·Trichloroethane 80% Other 18% HV=17685 THV=71. 2
Spent Solvent
3000 MT /Y r
\.Jater 0% Ash 2% Dichloromethane 80% Other 18% HV=15878 THV=12
121
0 3.01.03
Liquid
122
D 3.D1.04
Liquid
SIC 721
Spent Solvent
67000 MT/Yr
\.Jater 0% Ash 2% Tetrachloroethene 60% Other 38% HV=14978 THV=253
123
0 3.01. 05
Liquid
SIC 3471 SIC 3479 Metal Cleaning Operations
Spent Solvent
18000 MT/Yr
~ater 0% Ash 2% 1,1 1-Trichloroethane 22% Trichloroethylene 21% Hexane 31% Toluene 2% Dichloromethane 4% 1,1, 2, 2· Tetra.ch loroethane 7% Other 8% HV=7745 THV=35
SIC 3471 Metal Cleaning Operations
Oegreaser 14200 Sludge MT/Yr
124
D 3.01.06
X
125
D 3.01.09
Liquid
126
D 3.02.01
Liquid
127
D 3.02.02
Liquid
0 3.02.03
Liquid
128
1
\.Jater 10% Ash 20% 1,1,1·Trichloroethane 20% 1 1 2-Trichloroethylene 20% Other 30% HV=18072 ·THV=64.6 1
1
Spent Solvent
1500D MT/Yr
\.later 0% Ash 2% Toluene SOX Other 18% HV=13597 THV=51.3
Trichloroethylene Prod.
still Bottoms
18000 MT /Yr
\.later 0% Trichloroethylene 20% Other 80% HV=8606 THV=39
11 11 1•
Still Bottoms
15000 MT/Yr
\Jeter 0% Ash 20% 1, 1, l·Trichloroethane 20% Other 60% HV=8606 THV=32.5
Trichloro· ethylene Prod.
Methylene Chloride Prod.
Methylene 2000 Chloride MT/Yr St i l t Bottoms
A-ll
\.later 0% Ash 20% Oichloromethane 20% Other 60% HV=7702 THV=3,9
~ASTE
INFO. SOURCE
TYPE OF WASTE NONAO. LIOUIO/ AQUEOUS SOLI 0
HYDROCARBON COMPILATION (continued)
TYPE OF INOUSTRY/ PROCESS
Liquid
0
3.02.90
130
0
SOURCE OF WASTE Still Bot toms
Sludge
Paint
3.03.01
Sludge
Application
INOUS. TOTALS 15000 MT/Yr
29000 MT/Yr
WASTE CHARAC./COMMENTS \.later 0% Ash 20% Toluene 20% Other 60% HV=5895 THV=22.3 \.later 25%
Ash 20% MEK 1% Toluene 1%
Heavy Metals 0.01% Other 54% HV=10886 THV=79.4 131
0
Liquid
3.04.01
SIC 2865
Benzyl
still Bottoms
8380 MT/Yr
Heavy Ends
6360 MT/Yr
Chloride
Prod.
132
0
Liquid
3.04.02
SIC 2869 Epichloro· hydrin
Prod.
133
0
Li.quid
3.04.03
SIC 2869 Ethyl
Fraction· 35400 ating MT/Yr
Chloride
Column
Prod.
134
0
liquid
3.04.04
SIC 2869
Heavy
Ethylene
Ends
0
Liquid
3.04.05
0
3.04.06
Liquid
Yater 0%
Ash 10% 1,2·Dichloropropane 10% Epichlorohydrin 2% Other 78% HV=3744 THV=6.0 \.later 0% Ash 2% 1,2·Dichloroethane 11% Hexachlorobenzene 22% Hexachlorobutadiene 22% Trichloroethylene 32% Other 11% HV=2754 THV=24.5
\.later 0% Ash 5% 1,2-Dichloroethane 21% 1, 1, 1,2-Tetrachloroethane 12% 1, 1,2,2-Tetrachloroethane 12% 1, 1,3-Trichloroethane 24% Other 26% HV=4002 THV=80.9
SIC 2869
Heavy
Vinyl Chloride
Ends
52700 MT/Yr
\Jater 0% Ash 5% 1,1, 1,2-Tetrachloroethane 21% 1, 1,2-Trichloroethane 27% 1,2-Dichloroethane 24% Vinyl Chloride 0.2% Other 23% HV=4002 THV=53.1
Light Ends
760 MT/Yr
\.Jater 0% Ash 10% Maleic Anhydride 90% Phthalic Anhydride 10% HV=6024 THV=1.2
Prod.
136
Ash 10% 1,2,4·Trichlorobenzene 0.4% Hexachlorobenzene 0.4% Toluene 0.3% Other 89% HV=12048 THV=25.4
80300 MT/Yr
Dichloride Prod.
135
\.later 0%
SIC 2865 Phthalic
Anhydride Prod.
A-12
~ASTE
TYPE OF INFO. lr.EM
137
~
AQUEOUS
D 3.04.07
HYDROCARBON COMP[LATION (continued)
~ASTE
NONAO. LIQUID/ SOLID Liquid
TYPE OF INDUSTRY/ PROCESS SIC 2865
SOURCE Of ~
'Light
Phthalic Anhydride
Ends
INDUS. TOTALS
2100 MT/Yr
Prod.
138
139
D 3.04.08
liquid
Liquid
D
3.04.09
SIC 2869 Hexamethylene Dlamine Prod.
5800 MT/Yr
~ASTE
CHARAC.[COMMENTS Yater OX Ash 2% Anhydride 83% Maleic Anhydride 17% HV=7315 THV=3.9 ~ater 0% Ash 10%
Cyclohexane 20% Other 70% HV=10843 THV=15.8
SIC 2865 Nitrobenzene Prod.
0 i still· at ion
1500 MT/Yr
Bottoms
\Jater 0%
Ash 2% m·Dinitrobenzene 31% Nitrobenzene 40% 2,4·Dinitrotoluene 19% 4·Nitrophenol 3%. Other 5%
HV=8993 THV=3.4 140
141
D 3. 04.10
Liquid
D 3. 04. 11
Liquid
SIC 2869 . Perchloro·
960 MT/Yr
Yater 0% Ash 2% Carbon Tetrachloride"93% Trichloroethylene 7% HV=2022 THV=0.49
ethylene
Carbon Tetra. Removal
Prod.
Effluent
SIC· 2869 Trichloro·
Heavy Ends
48400 MT/Yr
Yater 0% Ash 10% Wexachlorobenzene 20% Hexachlorobutadien e 34X 1,1,2,2-Tetrachlor oethane 23% 1,1, 1,2·Tetrachloroeth ane 6.3% Other 7% HV=4002 THV=48.8
ethylene
and Perchloro· ethylene
Prod.
142
0 3.04.12
Liquid
SIC 2865 Chlorobenzene Prod.
s t iII Bottoms
4500 MT/Yr
\.later 0% Ash 10% Hexachlorobenzene 10% Other 80% HV=602 THV=0.68
143
D 3.04.13
Liquid
SIC 2865 Phenol Prod.
Distill· at ion Bottoms
106200 MT/Yr
\.later 0% Ash 5% Phenol 0.9% Benzo(A)pyrene 0.1% Benzo(A)anthrocene 0.1% Chrysene 0.1% Other 94% HV=15060 THV=403
SIC 2869 Acetaldehyde Prod.
Distill· at ion Side Cut
26300 MT/Yr
\.later 47% Ash 2% Acetaldehyde 16% Chloroacetaldehyde 12% Chloroform 2% Formaldehyde 2% Other 19% HV=3313 THV=21.9
144
0
3.04.14
X
A-13
YASTE HYDROCARBON COMPILATION (continued)
TYPE
OF
INFO.
ITEM
~
145
D 3.04.15
AOUEOUS
~ASTE
NONAO. LIQUID/ SOLID Liquid
TYPE OF
SOURCE OF \.IASTE
INDUSTRY/ PROCESS SIC 2865
~
Aniline
i8oO
Bot toms
MT/Yr
INDUS. TOTALS
Prod.
~ASTE
CHARAC./COMMENTS ~ater
0.1% Ash 2% Aniline 91% Benzene 6% Nitrobenzene 2% Diphenylamine 0.1% Phenylenediamine 0.3% HV=15663 THV=7.1
146
D
3.04. 16
liquid
SIC 2869
Stream
1300
\.later 0%
1,1,1·Tri·
Stripper 'Waste
MT/Yr
Ash 2% 1,2-0ichloroethane 17% 1, 1,2-Trichloroethan e 83% HV=4991 THV=1.6
chloroethane Prod.
147
D
3.04.17
Liquid
SIC 2869
Heavy
1300
\.later
Maleic
Ends
MT/Yr
Ash 5%
Anhydride
Maleic Anhydride 12% Other 83% HV=3012 THV=2.7
Prod.
148
D
3.04.18
Liquid
SIC 2865 Cyclohexanol
Ends
5600 MT/Yr
\.later 0% Ash 5% Phenol 9% Other 86% HV=14200 THV=20
Light Ends
2700 MT/Yr
Yater 0% Ash 2% Benzene 45% Cyclohexanol 45% Other 8% HV=18933 THV=12.9
17300
Yater 0% Ash 2% Toluene 50% Carbon Tetrachloride 10% Other 38% HV=15921 THV=69.3
Heavy
Prod.
149
D
3.04.19
Liquid
SIC 2869 Cyclohexanol Prod.
150
D
3.04.20
Liquid
SIC 2865 Cyanuric
MT/Yr
Chloride Prod.
151
D
3.04.21
Liquid
SIC 2865 Benzene
22700 MT/Yr
Yater 0% Ash 5% Toluene 10% Benzene 10% Other 75% HV=17624 THV=101
101700 MT /Y r
Water 0.1% Ash 5% MEK 1% Other 94% HV=9509 THV=243
8200 MT/Yr
Yater 0% Ash 5% 1,3·Dichloropropen e 51% Other 44% HV=12048 THV=24.9
Prod.
152
D
3.04.22
Liquid
SIC 2869 Acetic Acid
Prod.
153
D
3.04.23
Liquid
0%
SIC 2869
Heavy
Allyl
Ends
Chloride Prod.
A-14
\.JASTE HYDROCARBON COMPILATION (continued)
TYPE OF INFO. SOURCE
AQUEOUS
D
~ASTE
NONAQ.
TYPE OF
LIQUID/ SOLID
INDUSTRY/
Liquid
3.04.24
PROCESS
SIC 2869 S·Butly Alcohol Prod.
SOURCE
OF
INDUS.
~ASTE
~ Light
TOTALS 22700
Ends
CHARAC./COMMENTS \.Jater 5%
MT/Yr
Ash 2% Methyl Ethyl Ketone 9% Other 84%
HV=14630 THV=83.6 155
0
Liquid
3.04.26
SIC 2869
Acetal·
Acrolein
1400
Yater 0.5%
de hyde Column
MT/Yr
Ash 2%
Prod.
Acetaldehyde 86% Acrelein 12%
HV=1162 THV=0.41 156
D
X
3.04.27
SIC 2869
4500
Water 36%
1, 1·0 imethyl·
MT/Yr
Ash 2%
hydrazine
Formaldehyde 2%
Prod.
Other 60%
HV=6497 THV=7.4 15 7
D
X
3.04.28
158
D
3.04.29
159
D
3.04.30
Liquid
Liquid
SIC 2869
Allyl
1400
Glycerin Prod.
Alcohol
MT/Yr
Recovery waste
SIC 2869
Heavy
Glycerin Prod.
820
Ends
MT/Yr
SIC 2869
Heavy
1600
Glycerin
Ends
MT/Yr
Prod.
'Water 40% Ash 5% Acrolein 24% 1,1-0ichloroethele ne 2.4% Other 29% HV=6670 THV=2.4 \.later 6% Ash 5% 2,·Chlorophenol 8% Other 81% HV=9897 THV=2.0 \.later 0.1% Ash 20%
Allyl Alcohol 3% Other 77% HV=5594 THV=2.3
160
D
3.04.31
Liquid
SIC 2865 Benzyl
still
680
Bottoms
MT /'(r
Chloride
61
D
3.05.02
62
D
3.05.03
Liquid SIC 2865 suspension
Liquid sus pen· sian
SIC 2869 1, 1, 1· Tri · chloroethane Prod.
Heavy
700
Bot toms
MT/Yr
0 i stilL· at ion Bottoms
35500 MT/Yr
A-15
\.later 0% Ash 10% Benzotrichloride 9% 1,2,4-Trichloroben zene 1% Hexachlorobenzene 1% Other 79% HV=12049 THV=2. 1 '..later 0% Ash 10% Phthalic Anhydride 45% Othe,~ 45% HV=9509 THV=1.7 \.later 0% Ash 10% 1, 1, 1,2-Tetrachloroeth ane 24% 1, 1,2,2·Tetrachloroe thane 27% Other 39% HV=2711 THV=24.2
WASTE HYDROCARBON COMPILATION (continued)
ITEM 163
164
INFO. SOURCE D 3.05,04
D 3.05.05
TYPE OF WASTE NONAQ. LIQUID/ AQUEOUS SOLID Liquid
Sus pen· sian
liquid
Sus pen· sian
165
166
D 3.05,06
0
3.05.07
TYPE OF INDUSTRY/ PROCESS SIC 2869 1 , 1 , 1 • Tr i chloroethane
SOURCE OF WASTE Heavy Ends
SIC 2865 Toluene Diisocyanate Prod.
Centri·
liquid
SIC 2865
Suspen·
Phthalic
sian
Anhydride Prod.
liquid
SIC 2869
Sus pen· sian
Glycerin
fuge &
INDUS. TOTALS
3200 MT/Yr
107900 MT /Yr
Yater 1% Ash 2% Toluene Diiscyanate 0.001% Toluene Diamine 0.0001% Other 97% HV=11015 THV=299
2500 MT/Yr
Yater 0% Ash 10% Phthalic Anhydride 36% Trichloroethylene 36% Other 18% HV=3012 THV=1.9
910D MT/Yr
Water 0% Ash 2% Sodium 54% Trichloropropane 13% Dichloropropanols 27%
0 i still· at ion
0 is till. at ion
Bottoms
Prod.
WASTE CHARAC.LCOMMEHTS Water 0% Ash 10% 1,1,2·Trichloroethane 27% 1, 1,1-Trichloroethane 27% Hexachloroethane 14% 1, l·Dichloroethane 17% Tetrachloroethane 14% HV=2469 THV=2.0
Other 3%
HV=2754 THV=6.3 167
0
3.05.08
168
169
170
D 3.05.09
D 3.06.01
D
3.06.02
liquid Sus pen· sion
SIC 2869 1, 1, 1 · Tr i · chloroethane Prod.
Spent Catalyst
610 MT/Yr
Yater 0% Ash 20% 1,1,3-Trlchloroethane 40% Acetyl Chloride 27% 1,1,2,2-Tetrachloroethane 32% HV=2582 THV=0.4
Liquid
SIC 2869 linear Alkyl Benzene Sulfonate Prod.
Distitl· at ion Bottoms
43650 MT/Yr
Yater OX Ash 2% Naphthalene 20% Other 78% HV=11618 THV=128
Liquid
SIC 2812 Chlorinated Hydrocarbon
Pur if i · ca i ton
340 MT/Yr
Yater 0% Ash 2% Chloroform 74% Carbon Tetrachloride 11% Other 13% HV=1119 THV=0.1
liquid
SIC 3312 Coking Operation
Decanter Tank
39800 MT/Yr
Yater 0% Ash 20% Naphthalene 15% Other 65% HV=14200 THV=142
Sus pen· sian
A-16
~ASTE
TYPE OF ITEM 171
INFO. SOURCE
ACUEOUS
0
HYDROCARBON COMPILATION (continu ed)
~ASTE
NotfAQ. _ LICUIO/ SOLID Liquid
TYPE OF INDUSTRY/ PROCESS
Solid
Liquid Sus pen· sian
PCB Fluids
INDUS. TOTALS 4500 MT/Yr
YASTE CHARAC./COMMENTS Yater 0% Ash 2% PCB·1254 50% 1,2,4-T richloro benzen e 50% HV=9897 THV=11.2
SIC 2992 Oil Re· Refinin g
Spent Clay
69000 MT /Yr
~ater
SIC 2992 Oil Re· Refinin g
Acid Tar
32000 MT/Yr
~ater
SIC 2992 Re· Refinin g
Caustic Sludge
9000 MT/Yr
\Jater 60% Ash 20% Lead 2% Benzo(A )pyrene 1% Benzo(A )anthrac ene 4% Other 13% HV=9036 THV=20.5
3.06.03
172
0
4.02.01
173
174
D 4.02.02
X
0
4.02.03
SOURCE OF ~ASTE
0% Ash 70% Lead 4% Benzo(A )pyrene 1% Benzo(A )anthrac ene 1%. Other 24% HV=3012 THV=52.3 10% Ash 20% Lead 1% Benz.o(A )pyrene 1% Benzo(A )anthrac ene 1% Other 67% HV=8606 THV=69.3
REFERENCES AND NOTES A B
C
0
Hazardo us Waste stream from the Industr iat Erickso n, D. F. ~ !1; I T Enviros cience, Survey of Potenti al Organic Chemica l Industr y, USEPA Cincinn ati, Ohio, May 1981. Compos ition of Hazardo us Waste Streams ; USEPA, Washing ton Haus, S. et ~; Mitre Corp; Draft Report D.C., November 1981. PURDUE INDUSTRIAL ~ASTE CONFERENCES (1) Groves S.E. and Lundgre n H.E., Part 1, Pages 99·108, 1973. (2) Foltz V.W., Part 1, Pages 314·321 , 1970. (3) Kato K. and Ishikaw a S., Part 1, Pages 610·619 ·, 1969. (4) Hugh M.J. and Dee T.M., Pages 571·576 , 1980. (5) Hunter R.A., Pages 115·120 , 1919. (6) Helsel R.Y., Pages 1059·10 67, 1976. (7) Cardile R.P., Pages 359·404 , 1981. (8) Gambhir S.P. tl ~; Pages 203·206 , 1982. Base; USEPA Office of Solid Waste, SCS Enginee rs, Draft Report W·E-T Model Hazardo us Waste Data Washing ton D.C., July 21, 1983. pound, Notes: HV= gross heat of combus tion of total waste in BTU per on 8760 hors per year. based hour per BTU of s million in value THY= total heating (*)
The heating value of waste hydroca rbon is estimat ed by RECON.
A-17
APPENDIX B WASTE EXCHANGES
B-1
Summaries of State and Regional Waste Exchange Programs
Colorado Waste Exchange 390 Logan Street Denver, CO 80203 303/831-7411 Contact: Olie Webb Type of Exchange: Information Profit Status: Nonprofit The Colorado Waste Exchange is sponsored by the Colorado Association of Commerce and Industry. Mr. Webb was not available. The staff available, at the time of our two phone contacts, was not familiar with products listed by the Colorado Waste Exchange.. No back issues of Exchange Bulletins were available.
Piedmont Waste Exchange Institute of North Carolina Charlotte, NC 28223 704/597-2307 Contact: Mary McDaniel Type of Exchange: Information Profit Status: Nonprofit The Piedmont Waste Exchange is a service of the Waste Information Research and Education Program of the University of North Carolina. It is sponsored by the Urban Institute and provides information, research and educational services to assist Carolina industries to develop safe, economical waste management strategies. About ten organic liquids (solvents) were listed in the quarterly Bulletins we reviewed. Of these solvents, only one was both continuous and in a quantity (more than a few drums per month) likely to make it worth transporting.
8-2
TECHRAD Indust rial Waste Exchange 4619 Santa Fe Oklahoma City, OK 73118 405/528-7016 Contact: David Trimberger Type
of Exchange: Inform ation; Laboratory Servic es; Engineering Consulting Service s ·
Profit Status : Profit TECHRAD Indust rial Waste Exchange was started about 18 months ago. To date, the Exchange has not been very succes sful. Because most listing s are combined stream s, they are difficu lt to exchange. No non-halogenated liquid hydrocarbons have been offered for exchange. The halogenated liquid hydrocarbons offered to date have been too contaminated for use.
Chemical Recycle Information Program 1100 Milan Building Houston, TX 77002 713/651-1313 Contac t: Jack Westney Type of Exchange: Information Profit Status : Nonprofit The Chemical Recycle Information Program, sponsored by the Houston Chamber of Commerce, began as a service to industr y in 1976. Inquir ies, compiling the monthly inventory list and mailing are handled by secreta rial staff. Most listing s are from Gulf Coast firms. These include a number of fuel potent ial waste solven ts offered in quanti ties and frequen cies that make them good candid ates for some type of fuel use depending on composition.
8-3
Intermountain Waste Exchange P.O. Box 1825 Salt Lake City, Utah 84110 801/295-5511 Contact: Joe Parkinson Function: Manages other exchanges According to Mr. Parkinson, the Intermountain Waste Exchange deals mostly with acid solvents. Of the organic solvents, only methylene chloride is reprocessed in California, Texas or Denver.
Southern Waste Information Exchange P.O. Box 6487 Tallahasse, FL 32313 904/644-5516 Contact: Dr. Roy Herndon Type of Exchange: Information Profit Status: Nonprofit Of the fuel potential wastes handled by the Southern Waste Exchange, Dr. Herndon felt there is always a market for used oils including service station contaminated waste oils that were generally sent to re-refi ners. Although no records are kept, Dr. Herndon estimates that 10 million pounds of liquid organic wastes are exchanged through the Southern Waste Exchange each year. Of the six waste liquid organics, listed in a sample quarterly catalog under the categories "Organic Chemicals, Solvents" and "Oils and Paints", no continuous large sources were described. A possible-exception is an inexplicit listing "Pump oil, epoxy paint" that showed "several" drums per month (segregated). Two listings of recycled solvents for sale were found. Nine requests to receive waste oils and non-halogenated solvents indicate a good market for those products. A single request for chemicals for reclamation was cited. Of the
B-4
waste liquid halogenated.
hydrocarbons
offered
for
exchange,
three
were
Virginia Waste Exchange 611 East Franklin Street Richmond, VA 23219 804/644-1607 Contact: Margaret Rush Type of Exchange: Information Profit Status: Nonprofit The Virginia Waste Exchange, a service of the Virginia State Chamber of Cornnerce, published its first catalog in August 1982. Unlike most catalogs, the Catalogs are issued twice annually. Virginia Waste Exchange Catalog contains offerings of large quantites of wastes on a continuous basis ( 1 oil, 2 chlorinated solvents and 3 organic solvent suppliers); this can probably be attributed to the newness of the exchange in Virginia. Experience of other exchanges indicates 'that if these materials are of usable quality, they will be "Materials Wanted'' listings appeared in all three exchanged. catagories. Ms. Rush measured the success of the exchange by a recent survey. Based on a 70% response, ten of the 125 May listings_ were successfully exchanged. A higher rate of success can be projected if one considers that successful exchanges are due to a previous catalog This is not an unreasonable that contained only 73 listings. assumption since exchanges often take more than 90 days.
B-5
Enkarn Research Corporation P.O. Box 590 Albany, NY 12201 518/436-9634 Contact: J.T. Engster Type of Exchange: Information Profit Status: Nonprofit The Enkarn packaging.
Research
Corporation
handles
only
textiles
and
Atlantic Coast Research Exchange Research Triangle Operations 1905 Chapel Hill Road Durham, NC 27707 919/493-3536 Contact: Gerhard Gschwandtner Type of Exchange:
~nformation
Profit Status: Profit Although the Atlantic Coast Research Exchange is no longer active (endeavor was not profitable due to size of supplies and purity guarantee of suppliers), Mr. Gschwandtner was willing to relate his experiences with the Exchange. He felt that organic solvents are always in demand by recyclers who sell them for printing ink, solvents, cleaning and degreasing solvents, paint strippers and photofinish ing solvents. He also believes that there is a great deal of waste, including organic solvents, that is disposed of by small generators. Economics and small generator status ~ake disposal rather than exchange or recycling the simplest alternative .
B-6
Great Lakes Regional Waste Exchange Waste Systems Institute, Inc. 3250 Townsend, N.E. Grand Rapids, MI 49505 616/363-7367 Contact: William Stough Type of Exchange: Information Profit Status: Nonprofit Similar to many European waste exchanges, the Great Lakes Regional Waste Exchange lists materials in a bimonthly industrial publication, Great Lakes Waste and Pollution Review Magazine. Listings are solicited from Illinois, Indiana, Michigan, Minnesota, Ohio and Wisconsin, with some contributions from Canada. This exchange was formed in early 1983. A sample catalog from the Great Lakes Waste Exchange showed that fifteen of the sixteen oil streams and many of the organic streams (21 of 43) were offered on a continuous basis. Fourteen of the oils offered appear to be recyclable or directly usable as a fuel. Ten non-halogenated liquid organic, five halogenated liquid organics and one amino liquid organic were offered on a continuous basis. In the same issue, there· were seven requests for oils, ten for general solvents, and five for chlorinated solvents. Most requests are for unlimited quantities. No study of success rate has been carried out to date.
5-7
Zero Waste Systems, Inc. 2928 Poplar Street Oakland, CA 94608 415/893-8257 Contact: Duncan Maclleny Type of Exchange: Material Profit Status: Profit The Zero Waste Systems, Inc. purchases materials that they believe are marketab le. Materials may be repackaged and sold as is, or refined to a higher grade product. Although a minimum quantity could not be specified , large quantitie s are preferred . Unused products can be resold for original use; reprocess ed products may be returned to originato r or elsewhere ; some products are sold as solvent blends. Some of the end uses Mr. Maclleney was aware of for his organic liquid products are in the cleaning, painting paint 1 manufact uring, autobody industrie s and for fuel (usually kiln). Mr. Maclleney had just completed a study which estimated thp.t 5,000 gallons of liquid organics are recycled by his firm every two months, with an average of 16,000 BTU's/ga l. Mr. Maclleney pointed out that hinderenc es to recycling and exchangin g included non-segre gation of streams, low cost of virgin aliphatic s, mineral spirits and naphthes, and the ability to burn liquid hydrocarb on wastes for fuel with little or no pretreatm ent.
B-8
American Chemical Exchange 4849 Go 1f Road Skokie, ll 60076 312/699-2000 Contact: Jeff Starky Type of Exchange: Materials Profit Status: Profit The American Chemical Exchange deals in streams of "significant" volume.
No bulletin is published. Products for known markets on a
continuous basis are sought.
Types of liquid organics dealt with
include alcohols, antifreeze, windshield cleaner and hydraulic brake fluid. Mr.
These are purified and resold. Starky felt
that
in the last three years
the recycling
industry has been changing. Smaller reprocessors have been driven out or bought out by larger firms.
Chemical producers have departments
that analyze and find appropriate uses for process byproduct streams. He stated that large volume waste organic streams are still reprocessed.
B-9
~ot
being
California Waste Exchange 2151 Berkley Way Berkley, CA 94708 415/540-2043 Contact: William Qwen Type of Exchange: Information Profit Status: Nonprofit The California Waste Exchange is a part of the Hazardous Waste Management Branch of the California Department of Health Services. The Exchange pub 1i shes a Newsletter/Catalog, a directory of industrial recyclers, and can provide staff, on request, to aid a company exploring recycling options for their waste streams in both regulatory and technical areas. California can, by law, require a company to justify choosing the disposal option over recycling of industrial byproducts. The Hazardous Waste Management Branch reviews waste manifests required by state law (more inclusive than RCRA) and contacts companies when the department feels justification for disposal is necessary. This legal requirement probably increases the number of waste products exchanged in California. Mr. Qwen estimated waste exchanged, via the California Waste Exchange in 1982, ranged from 23-24,000 tons comprising 140 transfers. In addition, the department reported that manifest instigated Departmental inquiries and other efforts led to recycling of the following liquid organics: Oil - 1700 tons Liquid hydrocarbons - 2500 tons Liquid halogenated hydrocarbons - 600 tons·
S-10
Georgia Waste Exchange 181 washingto n Street,
s.w.
Atlanta, GA
30303
404/223-22 64 Contact: R.D. Sumner Type of Exchange: Informatio n Profit Status: Non-Profi t The
Georgia
clearingho use
Waste
funded Industry Associati on.
Exchange
by
the
is
Georgia
an
informatio n
Business
and
sole function of the exchange is to publish a quarterly listing of waste available and waste sought. Because there is no mechanism for Th~
feedback to the waste exchange of actual transactio ns, no statistics or estimates of success are available . Sample liquid hydrocarb ons offered were liquid bottoms from solvent reclaimin g stills and PCB contamina ted mineral oil. From the descriptio n, these are probably sought by recyclers , although no informatio n on suppliers or recipient s is available . No records of materials listed is maintaine d. Available informatio n is from past issues of the bulletins .
B-11
Insustrial Materials Exchange Service 2200 Churchill Road, Springfield, Illinois
62706
217/782-6760 Contact: Julie Barrow Type of Exchange: Information Profit Status: Non-Profit The
Industrial
in
listing
EPA
Illinis
co-sponsored by the Chamber of ,commerce. included
Exchange
Materials
and
Material
transfer
expiration
notices
successful transfers.
Service the
Illinois
surveys to
is are
document
These surveys have provided the
following information on waste liquid hydrocarbons. Continuous Materials Transfers 1982 Material
Quantity/Year Savings/Year
Paint solvents
40,000 gal
$15,000
Water Soluble Oil
25,000 gal
10,000
*Mixed Solvent Solution
27,500 gal
2,750
5,000 gal
5,000
*Various Solvents
100,000 gal
75,000
*Solvents
Unavailable
6,000
Methyl Ethyl Ketone (MEK)
1,440 gal
12,000
Methylene Chloride
1,320 gal
12,000
106,000 gal
23,400
Toluol Sludge
58,000 gal
10,200
Trichloroethane Solution
u;; 200
*Paints
Waste Oils
gal
3,000
1,320 gal
1,100
16,500 gal
14,400
266,700 gal
93,300
Stoddard Solvent Flammable Solvent Mineral Spirit Solvent
B-12
Mater ial
Quant ity/Ye ar
High Aroma tic Oil Oils and Greas e
120,48 0 gal 106,00 0 gal
Saving s/Year 51,800 unava ilable
One Time Trans fers 1982 Solve nt Soluti on
6,000 gal
1,000
Fuel Oil
9,000 gal
4,050
Curre nt Listin gs Ms.
Barrow
indica ted
that
most
purch asers
of
liquid hydro carbon s are reclai mers who proce ss oil and organ ic solve nts for use as secon dary fuels. Conta minate d solve nts from the paint indus try p.re not often sough t becau se they are consid ered too thick for use.
B-13
Louisville Area Waste Exchange 300 West Liberty Street, Louisville, Kentucky
40202
502/582-2421 Contact: Stan Lampe Type of Exchange: Information Profit Status: Non-Profit The Louisville Area Waste Exchange is operated by the
staff
of
the
Governmental
Affairs
Group
of
the
Louisville Area Chamber of Commerce.
The exchange does
not
negotiations.
participate
serves then
only
to
seller/purchaser
forward
initiates
purchasers.
in his
own
Exchange
per year.
An
inquiries
to
the
negotiations
listings are
item appea-rs
It
seller,
with
who
potential
sent out
six
times
in three consecutive issues
for a single flat rate. No followup surveys are performed, consequently no statistics
on
available.
the_ success
Based
upon
rate
his
listings and correspondence, 100,000
to
300,000
quarterly. paint
and
gallons
Most of varnish
Louisville
area.
changing
economical
Mr. Lampe estimated that
industry
solvents
are
that make
is up
from the
prevalent about
80%
in
the
of
the
in the last year and attributes this the
reclaim
their
own
offered,
Mr.
Lampe
and
regulations
paint
and
solvents. estimated
making
varnish
Of
the
at
least
50%
information is available,
B-14
Mr.
it
industry
organic
and the next largest category was toluene. detailed
exchanged
Mr. Lampe has noticed a decrease in
economics for
is
handling
the solvents offered are
listings annually. to
exchanges
experience_ in
of
Solvents
solvent offerings
of
more to
solvents
was
xylene
Although no
Lampe estimates
5-10%
of
the
single
quantity
solvents
offered
are
exchang ed.
Most continuo us offering s are only listed once, because once a buyer is found, there is no need to continue listing unless the seller wishes to obtain a higher price. The exchang e rate may be high after a regular buyer is found, however the Exchange does not have data on volumes transfer red. Accordin g to Mr. Lampe most solvents are purchase d on the basis of their BTU value for boiler fuel.
B-15
Environmental Quality Control, Inc. 1220 Waterway Blvd.,
Indi~napolis,
IN
46202
317/634-2142 Contact: N.L. Beck Type of Exchange: Information Profit Status: Non-Profit Environmental process
of
Quality
mer:ging
Exchange and was
with
unable
Control
the to
Midwest send
·infor:mation.
B-16
Inc.
is
in
Industrial
catalogues
the Waste
or supply
New Engla nd Mate rials Excha nge P.O. Box 947, Kenne bunk, Maine
04043
207/9 85-61 16 Cont act: Miss D.L. Trask Type of Excha nge: Infor matio n Prof it Statu s: Non- Profi t The
New
acids
Engla nd Mate rials Excha nge lists mostl y and metal sludg es becau se indus tries produ cing
these
waste
are
preva lent
in
the
area.
Altho ugh no stati stics are main taine d, Miss Trask felt the succe ss of excha nges was direc tly relat ed to the time she spent locat ing recip ients . She estim ated succe ss rates betwe en 5-10% with littl e effor t and up to 15-20 % with consi derab le effor t on her part. The excha nge has been inact ive for the last few month s and will remai n so a few month s longe r await ing new fundi ng.
B-17
Northeast Industrial Waste Exchange 700 East Water Street Syracuse, New York 13210 315/422-6572 Contact: Walker Banning Information Type of Exchange: Profit Status: Non-profit
The Northeast Industrial Exchange is sponsored by the Central New York Regional Planning and Development Board and the Manufacturer s Association of Central New It
York.
serves
New
York,
New Maine, Pennsylvania , Vermont and is adding Ohio.
New
Jersey,
Hampshire,
Maryland,
Massachuset ts,
the Northeast Industrial Exchange, has conducted two follow up studies to gauge One study, documenting the success of· the Exchange. Mr.
Banning,
manager of
first si'x months of operation, August 1981 to January 1982, indicated organic chemicals and solvents were listed by nearly every type of company (22% of the total listings). Most inquiries were sent by companies located in heavily industrialize d areas to companies in similar areas. Companies receiving one or more letters of inquiry Results of the survey (a 48% response were surveyed. was obtained) indicated that more organic chemicals and solvents were sold than any other category. Thirteen exchanges
were
made
totaling
267
tons
of
material
valued at $90,000. This represents 60% of the number of
B-18
exch ange s,
9%
by
weig ht
Foll owin g
is
a
and
38%
by doll ar valu e of repo rted succ essf ul exch ange s. At the time of the surv ey, an add ition al fifte en of the forty -sev en listi ngs bein g nego tiate d were orga nics and solv ents . brea kdow n
of
liqu id
hydr ocar bon
"sol d": Amo unt (Ton s)
Esti mate d Valu e ( $)
*Ace tone
.6
*Sol vent
10.0
none $
2,04 0
*Tri chlo roet hane
3
*Tri chlo roet hane
3
1,10 0
197
49,0 00
5
'3, 0 0 0
Solv ents Ethy lene glyc ol Mixe d Ethy lene /gly cols
none
16
unkn own
* Indi cate s a one time only exch ange .
The surv ey also indi cate d that clas sific atio n of a wast e as haza rdou s did not affe ct its chan ces for exch ange . In
the
wast e
want ed
cate gory ,
only
one list ing com plete d a tran sact ion. A sing le requ est for solv ents resu lted in purc hase of 7,64 0 gall ons from five sepa rate sour ces valu ed at $35, 000. Neg otia tion s for thre e othe r solv ents were in prog ress at the time of the surv ey.
B-19
The conducted
Northeast a
study
I.ndustr ial of
the
Waste
Exchange
exchange
also
transactions
resulting from 1982 listings. Again, organic chemicals listing category the dominant and solvents were (19%) of the materials accounting for forty-eight offered, and two hundred and eleven (29%) inquiries related to forty-three of these listings. The organic and solvents category accounted for twenty-one (26%) of the listi.ngs requesting materials, but received only one hundred and forty three (28%) of the inquiries in the
"wanted"
category.
At
least
one
inquiry
was
This indicates that while received for cash listing. many companies are seeking waste organic and solvents In the oils, relatively few offerings are available. fats and waxes category, eleven of the twelve offered wastes received one or more of the fifty-one inquiries. In the waste category all twelve of the requests for materials received one or more of the fifty-one Again indicating competition for available inquiries. materials. A survey
companies receiving one or more inquiries into organics and solvents resulted in a 56% response from materials available listers and a 67% of
listing
response from materials wanted listers. Of the reported listings, 13% of the materials available listings ended in sale, 17% were still being negotiated and 70 % were Following is a breakdown of these not exchanged. materials by type and selling price:
b-20
Amount (Tons)
Material
Estimated Value ($ )
Organics/Sol vents Paint Thinner Trichloroeth ane Alcohols
42
14,000
2
385
unknown
Solvents
unknown
210
110 '000
10
unknown
Oils Various Oils
B-21
APPENDIX C INFORMATION FROM U.S. ENVIRONMENTAL PROTECTION AGENCY
C-1
Regional EPA Offices In
1980,
the
(characte ristics the
handling
of
EPA
U.S.
and such
defined
specific) wastes.
and
hazardous set
wastes
standards
for
was
the
Initially
it
responsib ility of the Regional EPA offices to see that states complied with federal guideline s, with the idea that as each state developed its own conformin g responsib ility would be relinquish ed by the region to the states. Many of the states have since become responsib le for their own programs leaving the regional offices with a monitorin g
hazardous
waste
program
that
function. Due to the planned transfer of responsib ility to the states and agency budget cuts, Regional EPA waste hazardous tracking been not have Off ices manifests . Although states have collected and reviewed hazardous waste informatio n and the forms are available for viewing, the informatio n has ncit been cpmpiled by most states.
C-2
The
include
bases
purpqrted
states
to
Massachusetts,
have
computerized
New
York,
date and
Kansas
California. Other Federal EPA Sources of Information include a General Survey of Hazardous Waste Facilities taken in 1980 and the computerized data base from RCRA Part A which
estimates
Information
the
hazardous both
regarding
of
wastes
to
be
these sources
handled. is
being
pursued. The Regional
u.s.
EPA offices were surveyed.
The
results of this survey are briefly discussed below.
Bill Torey Region I EPA JFK Bldg. Waste Management Division Boston, Massachusetts 02203 617/223-4448 (Connecticut, six states in Region I Massachusetts,· New Hampshire, Rhode Island, Vermont and Maine), only Massachusetts has a computerized data base The other five states for hazardous waste tracking. track hazardous wastes but have not computerized their system. Since all six states are authorized, the region has no information on specific hazardous waste types Of
the
and quantities in the region.
C-3
Jim Reidy EPA Reg ion II Solid waste Branch 26 Federal Plaza New York, NY 10278 212/264-05 04 Mr.
Reidy
indica ted
that
both
New
York
and
New
Jersey are authorize d to control their own hazardous waste programs. New York has a computeri zed manifest system and New Jersey is the in process of computeri zing their manifest system.
Shirley Bulkin EPA Region I I I Hazardous Materials Branch 6th and Walnut Streets Philadelp hia, PA 19106 215/579-98 14 Ms.
Bulk in
indica ted
she
was
not
aware · of
any
computeri zed hazardous waste informatio n at the state level Cfor Maryland, Pennsylva nia, Delaware, Virginia, and West Virginia) , but the Permit Applicatio n Part A for hazardous waste quantitie s for the computeri zed the by washingto n, D.C.
facilitie s, subsequen t Waste
C-4
which
year, Managemen t
estimated had Branch
been in
Rita Ford EPA Region IV Residuals Management Branch 345 Courtland Street, N.E. Atlanta, GA 30365 404/881-3067 In
Region
IV,
Alabama,
for
delegated
regulations.
Phase
Although
South
Carolina,
Florida and Mississippi have
North Carolina, Kentucky, been
Georgia,
I
of
periodic
the
hazardous
waste
of
state
overviews
actions are performed by the regions, Ms. Ford was not aware of any computerized lisitngs for any of the Region IV states.
Marilee Hood Region VI EPA Solid Waste Branch 1201 Elm Street Dallas, TX 75270 214/767-9725 New
Mexico,
Oklahoma,
Arkansas,
Louisiana,
and
Texas will have RCRA authorization as of September 30, Ms. Hood was not aware of any states having 1983. computerized hazardous waste information.
C-5
Jane Radcliffe Region VII EPA Air and Waste Management Division 324 East 11th Street Kansas City, MO 64106 816/374-6534 All
of
the
Region
VII
states
(Nebraska,
Iowa,
Kansas and Missouri) are authorized to handle their own hazardous waste programs, therefore, no manifests go to the
regional
process,
a
office.
During
the
facility which stores,
original
generates,
permit handles,
or disposes hazardous wastes must identify the wastes to
be
handled.
Once
permitted,
facilities
are
not
required to notify states of any changes in materials handled
except
additions.
Only
Kansas
computerized data base for hazardous wastes.
C-6
has
a
U.S. EPA Region VIII Waste Management Branch 1860 Lincoln Street Denver, CO 80295 303/837-2221 Contact: John Minkoff states, Mr. Minkoff stated that only Colorado had Of the six Region Results from computerized data from hazardous waste manifest. analysis of these data should be available in an annual report. The regional office does not require a copy of this informati on. However, each state in the region does require manifests and should have lists of treatment , storage and disposal facilitie s fo hazardous wastes. This informatio n for 1983 is expected to be computerized some time in 1984. Mr. Minkoff's experienc e indicated that many solvent sellers were getting into the recycling of their own products. Mr. Minkoff supplied a list of Hazardous Waste Recycling Faci1l~ies in Region VIII Three solvent recyclers are located in Colorado, one used oil recycler in Utah, and an EP toxic metals (K065) recycler in Wyoming.
C-7
U.S. EPA Region IX Hazardous Materials Branch 215 Fremont Street San Francisco, CA 94105
415/974-8391 Contact:Ms. Robinson Of
the
Region IX States,
only
California
has
computerized
Hazardous Waste Manifest data.
(These data, due to the number of requests, are not available at this time. California plans to design
a method for distribution of this information-before mak_ing printouts avai 1ab 1e.) The Region Office does not require copies of this information.
U.S. EPA Region X Waste Management Branch 1200 6th Avenue Seattle, WA 98101
201/442-2859 Contact: Mike Bussell Mr. Bussell was not aware of any state data bases on hazardous wastes. The Region X Office did not require specifics in this area. Annual reports from the states might be available.
C-8
APPENDIX D KEY WORDS FOR COMPUTERIZED SEARCH 1.
Hydrocarbon wastes Organic wastes Industrial wastes Subdescripto rs: Liquid Identificatio n of Treatment of Extraction of Recycling of
2.
Materials recovery wastes reclamation Recycling waste subdescripto rs: Liquid Hydrocarbon Organic
l'rU.S. GOVERNMENT PRINTING OFFICE: 1987-548-122/60007
0-1
