Section VI.

F: Chemical Production Processes

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Section VI.F. Guidance by source category: Annex C, Part III Source Categories Chemical production processes

Coordinated by

r. !illiam Carroll "International Council o# Chemical Associations$

Section VI.F: Chemical Production Processes

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Best Available Techniques-Best Environmental Practices (BAT-BEP) for Chemical Production Processes
1.0 Process escri!tion 1.1 Introduction to Organic Chemical Processes 1.2 Co-Product Hydrogen Chloride 1.3 irect Chlorination 1.! O"ychlorination 1.!.1 Fi"ed #ed O"ychlorination 1.!.2 Fluid #ed O"ychlorination 1.$ %ain Product Isolation 1.& #y-'roduct estruction 1.( Summary: )hat Organic Processes Ha*e In Common 1.+ Introduction to Inorganic Chemical Processes 1., -itanium io"ide ".0 Potential #ources of $nintentionall% Produced Persistent &r'anic Pollutants (P&Ps) 2.1 O"ychlorination Process 2.1.1 .cetylene Process /or Vinyl Chloride. 2.2 Other Process Contact 0ith 1lemental Chlorine 2.3 -itanium io"ide 2.! #y-Product estruction 2.$ Products (.0 Alternate Processes to Chlorination 3.1 -itanium io"ide2 Sul/ate Process ).0 Primar% and #econdar% *easures !.1 Primary %easures o/ 3reater Im'act !.1.1 istillation and Internal 4ecycling o/ #y'roducts !.1.2 1limination o/ Car5on 1lectrodes /or Chloral6ali !.1.3 1limination o/ .l6ali -reatment o/ 22!2$--richloro'henol. !.1.! 1limination o/ Phenol 4oute to Chloranil. !.1.$ %odi/ied Production o/ Pentachloro'henol and Sodium Pentachloro'henate !.2 Primary %easures o/ 7esser Im'act !.2.1 8se o/ Hydrogen in O"ychlorination !.2.2 Catalyst %aintenance and -em'erature 8ni/ormity Control !.2.3 4eduction in .romatic Hydrocar5ons in Feeds to O"ychlorination. !.3 Secondary %easures !.3.1 #.- /or )aste is'osal Practices +.0 #ummar% of *easures ,.0 Performance #tandards -.0 Performance .e!ortin' .''endi" .: Synthesis o/ Commodity Chemicals .''endi" #: Chlorine Product -ree

Section VI.F: Chemical Production Processes

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1.0 Process

escri!tion

1.1 /ntroduction to &r'anic Chemical Processes. -his 'a'er /ocuses on 'rocesses /or the manu/acture o/ large-*olume industrial chemicals 0hich could theoretically gi*e rise to 5y-'roduct POPs. Chlorination 'rocesses are used in synthesis o/ hundreds o/ industrial and s'ecialty chemicals.1 Chlorine chemistry is also used in 'rocesses 0here the /inal 'roduct contains no chlorine atoms. 8nder modern conditions o/ o'eration2 ho0e*er2 these 'rocesses are ty'ically not a ma9or source o/ emission o/ 5y'roduct POPs.223 %any o/ the general 'rinci'les de*elo'ed here can also 5e a''lied to the much larger num5er o/ manu/acturing 'rocesses used to 'roduce a 0ide range o/ /ine :lo0-*olume s'ecialty; chemicals2 including 'esticides and 'harmaceuticals. Production o/ such chemicals de'ends on the uni<ue 'ro'erties o/ chlorine that ma6e it a *alua5le synthetic tool. . list o/ some o/ the 'rocesses leading to industrial chemicals is included in .''endi" ..1 It is 5eyond the sco'e o/ this 'a'er to attem't to de/ine #.-=#1P /or each o/ these 'rocesses indi*idually> rather2 the 'rocesses 0ill 5e e"amined /or 0hat they ha*e in common and ho0 those common 'ractices can 5e addressed 5y #.-=#1P to reduce the /ormation and 'articularly the release o/ 5y-'roduct POPs. 0i'ure 1. 1eneral Process overvie2

&

Section VI.F: Chemical Production Processes

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0i'ure ". C1 and C" !rocesses.1

'

Section VI.F: Chemical Production Processes

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%ost o/ the 'rocesses in*ol*e a hydrocar5on2 saturated or unsaturated2 treated 0ith elemental chlorine and in most 'rocesses also a catalyst. 4eactions can 5e electro'hilic additions to ole/ins2 chlorination o/ aromatics2 or homolytic clea*age o/ car5on-hydrogen 5onds 0ith su5se<uent /ormation o/ the ali'hatic chloride. In many cases2 chlorine atoms are 'resent in the /inal 'roduct> on the other hand2 in some 'rocesses :addition o/ an alcohol or amine to 'hosgene to 'roduce2 /or e"am'le2 'olycar5onate and 'olyurethane 'lastics; no chlorine atoms are 'resent in the /inal 'roduct. In addition2 most o/ the 'rocesses in*ol*e generation o/ HCl as a co-'roduct2 *ia dehydrohalogenation or /ree radical reaction o/ chlorine 0ith ali'hatic hydrogen :Figure 1;. Crude 'roducts o/ these reactions *ary in o*erall yield and 'urity2 and as 0ith *irtually all industrial chemical 'rocesses2 'uri/ication o/ the /inal 'roduct is re<uired 'rior to sale or /urther internal use. Puri/ication can in*ol*e se'aration o/ a mi"ture o/ sala5le 'roducts?in many cases a s'ectrum o/ use/ul 'roducts results /rom a single reaction treatment--or se'aration o/ sala5le 'roducts /rom the ine*ita5le /ormation o/ high molecular 0eight side 'roducts. For most organics and some inorganics that 'uri/ication ste' in*ol*es distillation. 3enerally2 high molecular 0eight side 'roducts are not sala5le as themsel*es. In some cases they are thermally o"idi@ed2 0ith HCl2 CO and CO2 as 'roducts o/ this o"idation. HCl is reco*ered and reused as an integral 'art o/ the 'rocess. In some cases they are *ie0ed as 0astes to 5e destroyed2 usually 5y ha@ardous 0aste com5ustion2 still2 HCl recycling is common. 1." Co-Product 3%dro'en Chloride. HCl is handled in one or more o/ the /ollo0ing 0ays. It can sim'ly 5e neutrali@ed and discharged as salt :sodium chloride;. Ho0e*er2 in some 'rocesses HCl can constitute a large amount o/ the e//ecti*e use o/ in'ut chlorine2 so neutrali@ation and discharge carries 0ith it a large o''ortunity cost in the loss o/ 'otential ra0 material. HCl can 5e reco*ered2 hydrated and then sold as the commercial 'roduct muriatic :hydrochloric; acid or used /or 'H ad9ustment in chloral6ali cells. -hus2 there is some recycling o/ HCl electrolytically to chlorine. %uriatic acid in the 8S has 5een analy@ed /or PC =F and /ound to contain ca. 2A 'g I--1B=7 range :A.AA! g I--1B=yr /or 8S 'roduction;.! HCl can also 5e dried2 o"idi@ed catalytically and in the 'resence o/ organic ra0 material2 reacted as elemental chlorine to generate more o/ the desired 'roduct. -he 'rocess 5y 0hich this is accom'lished is called o"ychlorination and o/ten constitutes a *alua5le means o/ in-'rocess recycling to a*oid 0aste o/ *alua5le chlorine /eedstoc6. 1.( irect Chlorination. Free radical addition o/ chlorine to ali'hatic hydrocar5ons2 ty'ically methane2 and direct electro'hilic addition o/ a halogen to an al6ene are 0ell6no0n /rom 5asic organic chemistry. .s utili@ed in industry2 the /ormer is cataly@ed 5y

Section VI.F: Chemical Production Processes

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light and the latter is ty'ically a lo0Ctem'erature o'eration cataly@ed 5y FeCl 3 .$ In the /ormer2 a /ree radical mechanism is desired. On the other hand2 in the latter2 un'roducti*e side reactions result /rom /ree radicals 0hich can 5e inhi5ited 0ith lo0 concentrations o/ o"ygen. -here is little i/ any 'otential /or /ormation o/ 5y'roduct POPs in direct chlorination 'rocesses o/ ali'hatic hydrocar5ons. .romatic /eedstoc6s can also 5e chlorinated directly under mediation o/ a 7e0is acid catalyst. -he 'resence o/ aromatic chlorides as 'roducts o/ the 'rocess lea*es o'en the 'ossi5ility /or POPs generation under some conditions. 1.) &4%chlorination. In o"ychlorination2 an organic such as ethylene reacts 0ith dry HCl and either air or 'ure o"ygen in a heterogeneous catalytic reaction. .n e"am'le is the reaction in*ol*ing HCl2 o"ygen and ethylene to /orm ethylene dichloride :1 C; and 0ater. C"3) 5 "3Cl 5 6&" 78 C"3)Cl" 5 3"& )hile there are many di//erent commercial o"ychlorination 'rocesses2 in each case the reaction is carried out in the *a'or 'hase o*er a modi/ied eacon catalyst. 8nli6e the eacon 'rocess :0hich o"idi@es HCl and O2 to Cl2 and H2O under heat and catalysis; o"ychlorination o/ ethylene occurs readily at tem'eratures 0ell 5elo0 those re<uired /or HCl o"idation per se. -he catalyst ty'ically contains cu'ric chloride :CuCl 2; as the 'rimary acti*e ingredient2 im'regnated on a 'orous su''ort such as alumina2 and may also contain numerous other additi*es. -he o"ychlorination reaction generates heat and thus re<uires cooling /or tem'erature control2 0hich is essential /or e//icient 'roduction o/ 1 C. )hile there is an e//ecti*e minimum tem'erature /or the reactions2 e"cessi*ely higher reactor tem'eratures lead to more 5y-'roducts2 mainly through increased ethylene o"idation to car5on o"ides and increased 1 C crac6ing. Crac6ing o/ 1 C yields *inyl chloride monomer :VC%; and su5se<uent o"ychlorination and crac6ing ste's can lead 'rogressi*ely to higher molecular 0eight 5y-'roducts 0ith higher le*els o/ chlorine su5stitution. 1"cessi*e tem'eratures :D3AAEC; can also deacti*ate the catalyst through increased su5limation o/ CuCl2. -here is a strong commercial incenti*e to a*oid those reaction conditions :o*erheating; that ha*e the 'otential to lead to the 'roduction o/ 'olychlorinated 5y'roducts. -here are t0o ty'es o/ catalyst systems used in o"ychlorination: /i"ed 5ed and /luid 5ed. #oth can 5e considered #.-.& 1.).1 0i4ed Bed &4%chlorination. Fi"ed 5ed reactors resem5le multi-tu5e heat e"changers2 0ith the catalyst 'ac6ed in *ertical tu5es held in a tu5esheet at to' and 5ottom. 8ni/orm 'ac6ing o/ catalyst 0ithin the tu5es is im'ortant to ensure uni/orm 'ressure dro'2 /lo02 and residence time through each tu5e. 4eaction heat is remo*ed

Section VI.F: Chemical Production Processes

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5y generating steam on the shell side o/ the reactor2 or 5y /lo0ing some other heat trans/er /luid through it. -em'erature control in these reactions is im'ortant. -he tendency to de*elo' hot s'ots in a /i"ed 5ed can 5e minimi@ed 5y 'ac6ing the reactor tu5es 0ith acti*e catalyst and inert diluent mi"tures in 'ro'ortions that *ary along the length o/ the tu5es2 so that there is lo0 catalyst acti*ity at the inlet2 5ut the acti*ity steadily increases to a ma"imum at the outlet. .lternati*ely2 tu5es can 5e 'ac6ed 0ith catalyst /ormulated to ha*e an acti*ity gradient along the length o/ the tu5es. %ulti'le reactors in series can also 5e used in /i"ed 5ed o"ychlorination2 'ro*iding a similar acti*ity gradient. Staging the air or o"ygen /eed and grading the catalyst acti*ity /latten the tem'erature 'ro/ile and allo0 im'ro*ed tem'erature control.( 1.)." 0luid Bed &4%chlorination. Fluid 5ed o"ychlorination reactors are ty'ically *ertical cylindrical *essels e<ui''ed 0ith a su''ort grid and /eed s'arger system designed to 'ro*ide good /luidi@ation and /eed distri5ution. -hey contain internal cooling coils /or heat remo*al2 and use either internal or e"ternal cyclones to minimi@e catalyst carryo*er. Fluidi@ation o/ the catalyst assures intimate contact 5et0een /eed and 'roduct *a'ors2 catalyst2 and heat trans/er sur/aces2 and results in a uni/orm tem'erature 0ithin the reactor. 4eaction heat is remo*ed 5y generating steam 0ithin the cooling coils or 5y 'assing some other heat trans/er medium through them. O'erating tem'erature o/ 22A-2!$EC and gauge 'ressure o/ 1$A-$AA 6Pa :22-(3 'sig; are ty'ical /or o"ychlorination 0ith a /luid 5ed reactor. Fi"ed 5ed o"ychlorination generally o'erates at higher tem'eratures :23A-3AAEC; and gauge 'ressures o/ 1$A1!AA 6Pa :22-2A3 'sig;. Chlorinated 5y-'roducts o/ ethylene o"ychlorination ty'ically include 12122-trichloroethane2 chloro/orm2 car5on tetrachloride2 ethyl chloride2 chloral2 2chloroethanol2 all o/ the chloroethylene congeners2 and higher 5oiling com'ounds.

Section VI.F: Chemical Production Processes

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0i'ure (. &4%chlorination 0lo2

ia'ram 9

1.+ *ain Product /solation. .nother common /acet o/ these 'rocesses is the need to 'uri/y 'roducts that 0ill either 5e sold or used in su5se<uent 'rocess ste's. In *irtually all cases2 organic reaction 'roducts 0ill 5e distilled. Fractional distillation se'arates streams o/ desired 'roducts and also desired 'roduct /rom un0anted high molecular 0eight materials called Fhea*y endsG or tars. In the 1uro'ean 8nion the Integrated Pollution Pre*ention and Control :IPPC; irecti*e re<uires the use o/ #est .*aila5le -echni<ues :#.-; in generating a 'lant 'ermit. -o /acilitate this2 #.- 4e/erence ocuments :#41Fs; are 'roduced under the irecti*e 5y the 1uro'ean Integrated Pollution Pre*ention and Control #ureau :1IPPC#;. Se*eral o/ these are rele*ant to the a''lication o/ #.- to 'rocesses using chlorination. For e"am'le2 the #41F relating to 7arge Volume Chemical Processes 'roduced under the IPPC irecti*e contains discussion o/ distillation. &

Section VI.F: Chemical Production Processes

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istillation is a standard engineering unit o'eration. It is 5ased on se<uential *a'ori@ation and condensation o/ li<uid in a column 0hich ty'ically includes 'ac6ing or trays so as to ma"imi@e its internal sur/ace area. Va'or that reaches the to' o/ the column is enriched in the lo0est 5oiling material 'resent in the distillation mi"ture. esign and o'eration o/ distillation units is 0ell-understood 5oth in se'arations theory and in 'ractice. For non-a@eotro'ing materials 0ith 0idely se'arated 5oiling 'oints?/or e"am'le2 *inyl chloride and PC =F--*irtually com'lete se'arations can 5e accom'lished in a 0ell-designed and o'erated column. , esired materials are isolated and trans'orted as li<uids. For materials 0ith 5oiling 'oints a5o*e am5ient tem'erature :e"am'le: 1 C; closed 5ut not 'ressuri@ed containers are used. For materials 0ith 5oiling 'oint 5elo0 am5ient tem'erature :e"am'le: VC%2 chlorine; 'ressuri@ed containers are used. 1., B%-!roduct estruction. 8ndesired materials2 including hea*y ends are destroyed in thermal 'rocesses2 0ith or 0ithout o"ygen. Figure ! sho0s a 'rototy'ical hea*y ends destruction train 0ith HCl reco*ery. )hen there are air2 0ater and solid emissions /rom this 'rocess2 these streams can 5e analy@ed and treated /or 5y-'roduct POPs contamination. 8nder the IPPC irecti*e2 #41Fs /or 0aste com5ustion and treatment o/ 0ater and gas out'uts /rom these 6inds o/ 'rocesses are 5eing de*elo'ed2 although treatment systems are 0ell-de/ined 5y regulation in many countries. In general2 #.- /or air streams can in*ol*e reco*ery and recycle o/ HCl2 com5ustion o/ trace *olatiles2 scru55ing o/ incinerator out'ut streams 0ith 0ater2 al6aline solutions or dry al6ali2 addition o/ acti*ated car5on and 5aghouses /or remo*al o/ 'articulate. -hese may 5e used alone or in com5ination. -reatment o/ 0ater streams can in*ol*e stri''ing and reco*ery :condensation or a5sor'tion; o/ *olatile materials /rom 0ater. Su5se<uent 5iological 'uri/ication o/ 0ater streams 0ith remo*al o/ solids is done in a dedicated 0ater treatment system. #.- /or 5oth streams 0ill 5e considered in the granting o/ 'ermits /or /acilities com5usting hea*y ends. 1.- #ummar%: ;hat &r'anic Processes 3ave /n Common. Figure $ summari@es generically many o/ the 'rocesses descri5ed2 including chlorination o/ organic or inorganic ra0 materials2 'uri/ication o/ the 'roducts2 se'aration o/ streams /or recycle :HCl2 %edium #oilers;2 destruction o/ side-'roducts :Organic High #oilers; and sale o/ 'roducts :7o0 #oilers2 HCl2 1nd Products;.

Section VI.F: Chemical Production Processes

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0i'ure ). B%-Product

estruction

0i'ure +. Bloc<

ia'ram of 1eneric &r'anic Process

-.

Section VI.F: Chemical Production Processes

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1.9 /ntroduction to /nor'anic Chemical Processes. Chlorine is used in generating inorganics 0hether it remains in the /inal 'roduct :HaOCl2 ClO 22 FeCl32 .lCl32 InCl22 etc.; or is sim'ly used in the 'rocess :-iO22 Si;. -hese inorganic com'ounds may 5e used either stoichiometrically :HaOCl2 ClO2; or as catalysts :FeCl32 .lCl32 InCl22 etc;. -hus /ar2 the only inorganic chemical manu/acturing 'rocess identi/ied 0ith 'roduction o/ 5y'roduct POPs is manu/acture o/ -iO2 5y the chloride 'rocess> ho0e*er2 other metal car5ochlorination 'rocesses /or 'uri/ication o/ ore may in*ol*e similar conditions to that o/ -iO2 'rocessing. 1.= Titanium io4ide. -here are t0o 'rocesses /or manu/acture o/ -iO2: the chloride 'rocess and the sul/ate 'rocess. -hey 'resent an interesting case study: the /ormer 'roduces much less 0aste 5ut under some circumstances can gi*e rise to POPs. -he latter in*ol*es much more non-POPs 0aste. -he chloride 'rocess has gro0n in use o*er the 'ast thirty years as a result o/ its relati*e com'actness2 recycling o/ 'rocess materials2 5etter 'roduct 'ro'erties and considera5ly lo0er generation o/ 0aste. -iO 2 ore such as rutile or ilmenite -- containing other metal o"ides--is chlorinated under high tem'erature to 'roduce -iCl !2 a sta5le2 distilla5le li<uid. Other metal halides are remo*ed a/ter cooling. -iCl ! is then 'uri/ied and o"idi@ed 0ith O22 li5erating chlorine2 0hich is recycled in the 'rocess. -his o"idation 'rocess is thermodynamically /a*ored at tem'eratures a5o*e &AA J C. . generali@ed o*er*ie0 o/ the chloride 'rocess is sho0n in Figure & and a more com'lete descri'tion o/ the com'eting sul/ate 'rocess is /ound in Section 3.1 0i'ure ,. Chloride Process for *anufacturin' Titanium io4ide.

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Section VI.F: Chemical Production Processes

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".0 Potential #ources of $nintentionall% Produced P&Ps. ".1 &4%chlorination Process. -he 'resence o/ heat2 elemental chlorine2 co''er chloride catalyst and t0o-car5on organic material ca'a5le2 in 'rinci'le2 o/ cyclotrimeri@ation :acetylene2 chloracetylenes2 ethylene2 chlorinated ethylenes; to aromatics ma6es the o"ychlorination 'rocess a 'otential source o/ 5y-'roduct POPs. .romatics may also 5e 'resent in /eed materials2 including air. Conditions in an o"ychlorination reactor are in some 0ays similar to conditions in the cooler areas o/ an incinerator.1A211 #y-'roduct POPs created in this 'rocess2 ho0e*er2 are *irtually com'letely isolated in high-5oiling materials :hea*y ends; rather than 'roduct as a result o/ the distillation 'rocess. Some 5y-'roduct POPs 0ill adhere to 'articles o/ catalyst. In the case o/ /i"ed 5ed systems2 they can 5e a 'art o/ the s'ent catalyst that is remo*ed /rom ser*ice. -his material can 5e treated thermally to destroy adsor5ed organics or 'laced in a secure land/ill. In reactors2 /luidi@ed 5ed catalyst 'articles undergo si@e attrition and can 5ecome entrained in the *a'or stream. -hese 'articles e*entually sho0 u' in solid 0aste or in the 5iological solids remo*ed at the end o/ 0ater treatment. ".1.1 Acet%lene Process for >in%l Chloride. 8se o/ the 5alanced 'rocess /or 'roduction o/ 1 C2 and su5se<uent crac6ing to *inyl chloride has2 o*er the 'ast $A years2 largely?5ut not entirely--su'erseded 'roduction o/ *inyl chloride *ia the acetylene route. In the acetylene 'rocess2 calcium o"ide and car5on are strongly heated together to 'roduce calcium car5ide. )hen CaC 2 is reacted 0ith 0ater2 acetylene is 'roduced. Vinyl chloride results /rom catalyst-mediated addition o/ HCl to acetylene. ue to the decreasing use o/ this 'rocess in the days o/ 0ell-de/ined analytical 'rocedures /or detection o/ POPs2 little is 6no0n o/ POPs generation and concentration in materials and 0astes. "." &ther Process Contact 2ith Elemental Chlorine. -here is anecdotal e*idence that contact o/ elemental chlorine 0ith organic 'rocess e<ui'ment :seals2 gas6ets2 /i5erglas e<ui'ment; can gi*e rise to 5y-'roduct POPs2 usually /urans. In certain 'rocesses 0here high 5oiling material or condensate is se'arated /rom manu/actured elemental chlorine and not recycled in the 'rocess2 5y-'roduct POPs can 5e /ound in solid or li<uid e//luent. ".( Titanium io4ide. -he 'resence o/ co6e2 chlorine2 metals and ele*ated tem'erature may gi*e rise to dio"ins and /urans analogous to those generated in o"ychlorination. PC =F2 i/ /ormed2 are e"'ected to 'artition into stream:s; containing residual co6e. ".) B%-Product estruction. -here are three ty'es o/ 0aste treatment: Ha@ardous )aste Com5ustion2 -hermal O"idation and Catalytic O"idation2 and some detail on each is 'resented in the 1 C=VC% Cha'ter o/ the 1IPPC# #41F on 7arge Volume Organics.& )hen hea*y ends are 5urned2 some 5y-'roduct POPs are generated as in any ha@ardous 0aste com5ustion. 1IPPC# is in the 'rocess o/ generating a #41F on

-%

Section VI.F: Chemical Production Processes

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0aste com5ustion 'rocesses> ho0e*er2 there are legal re<uirements and 5est a*aila5le technologies already in use in the 8S2 the 18 and Ka'an among others. -he Cato"idL12 'rocess is a /luidi@ed-5ed catalytic 'rocess /or o"idation o/ organics. It generates an HCl and CO2 stream that is sent in totality to the o"ychlorination reactor /or internal recycle. ".+ Products. %any 'roducts o/ these 'rocesses ha*e 5een analy@ed /or 5y-'roduct POPs2 es'ecially PC =F. In general2 'roducts o/ the chloral6ali-through-*inyl chloride chain are *ery lo0 in such contamination> ho0e*er2 /or these and other 'roducts the POPs concentration may 5e a /unction o/ the e//iciency o/ distillation or other 'uri/ication. (.0 Alternate Processes to Chlorination. (.1 Titanium io4ide? #ulfate Process. For -iO22 there is an alternate commercial 'rocess utili@ing sul/uric acid instead o/ chlorine. In the sul/ate 'rocess /or -iO2 ore is dried2 ground2 and classi/ied to ensure e//icient sul/ation 5y agitation 0ith concentrated sul/uric acid in a 5atch or continuous e"othermic digestion reaction. Controlled conditions ma"imi@e con*ersion o/ -iO 2 to 0ater-solu5le titanyl sul/ate using the minimum acid. -he resultant dry2 green-5ro0n ca6e o/ metal sul/ates is dissol*ed in 0ater or 0ea6 acid2 and the solution treated to ensure that only /errous-state iron is 'resent. -he solution tem'erature is reduced to a*oid 'remature hydrolysis and clari/ied 5y settling and chemical /locculation. -he clear solution is then /urther cooled to crystalli@e coarse /errous sul/ate he'tahydrate :6no0n as Mco''erasM2 FeSO!.(H2O; 0hich is se'arated /rom the 'rocess and sold as a 5y-'roduct. -he insolu5le MmudM is 0ashed to reco*er titanyl sul/ate li<uor. -hat li<uid is /iltered to remo*e /inal insolu5le im'urities2 then e*a'orated to a 'recise com'osition. Hydrolysis to 'roduce a sus'ension :M'ul'M; consisting 'redominantly o/ clusters o/ colloidal hydrous titanium o"ide /ollo0s. Preci'itation is care/ully controlled to achie*e the necessary 'article si@e2 usually em'loying a seeding or nucleating techni<ue. -he 'ul' is then se'arated /rom the mother li<uor and e"tensi*ely 0ashed to remo*e residual traces o/ metallic im'urities2 using chelating agents i/ necessary. -he 0ashed 'ul' is treated 0ith chemicals 0hich ad9ust the 'hysical te"ture and act as catalysts in the calcination ste'. -his 'rocess can 'roduce either anatase or rutile crystal /orms de'ending on additi*es used 'rior to calcination.13 )aste generation is /ar less in the chloride 'rocess2 5ut the chloride 'rocess may gi*e rise to small amounts o/ 5y-'roduct POPs. )aste generation in the sul/ate 'rocess2 including sul/uric acid and other mineral 0aste can 5e 1A-2A times higher2 5ut is not 6no0n to in*ol*e 5y-'roduct POPs. -rading elimination o/ small amounts o/ 5y-'roduct

-&

Section VI.F: Chemical Production Processes

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POPs /or generation o/ large <uantities o/ other 0aste materials may not 5e the o'timal en*ironmental a''roach. #.- can 5e 'lant s'eci/ic and *ie0ed on a case-5y-case 5asis. ).0 Primar% and #econdar% *easures ).1 Primar% *easures of 1reater /m!act ).1.1 istillation and /nternal .ec%clin' of B%-!roducts. istillation is used 'rimarily to 'roduce 'roduct o/ a 'urity a''ro'riate to do0nstream 'rocessing. .s an e"am'le2 VC% is manu/actured *ia o"ychlorination and 'uri/ied 5y distillation. 4igorous distillation is used due to the 'otential /or disru'tion o/ su5se<uent 'olymeri@ation 'rocess 5y im'urities. 8nsaturated materials that might act as co-monomers com'eting in the 'olymeri@ation and saturated or aromatic materials susce'ti5le to /ree radical reactions other than 'olymeri@ation can negati*ely im'act 'olymeri@ation reaction 6inetics. istillation and high 'urity are im'ortant /or good 'roduction. istillation systems can 5e designed to e//ect se'aration o/ materials o/ closely- or 0idely-se'arated 5oiling 'oints. -he 5oiling 'oints o/ chemical 'roducts o/ direct chlorination and the 5oiling 'oints o/ com'eting im'urities allo0 /or their 'ractical se'aration. -heir 5oiling 'oints are also su//iciently di//erent /rom those o/ the unintended POPs2 ho0e*er2 that *irtually com'lete se'aration can 5e accom'lished. -he 7arge Volume Organic #41F notes that 'uri/ied 1 C does not contain signi/icant amounts o/ PC =F. & estruction o/ chlorinated 5y-'roduct materials allo0s /or HCl to 5e har*ested and reused.1! -his is deemed Fgreater im'actG 5ecause small changes in POPs generation u'stream o/ distillation are not re/lected in the <uality o/ desired 'roducts a/ter distillation. istillation as a means o/ se'arating desired 'roduct /rom inad*ertent side 'roducts is used across the chemical 'roduction industry /rom commodities to 'esticides. .da'ting the design and o'eration o/ distillation a''aratus is2 in 'rinci'le2 relati*ely straight/or0ard. 4esidual side 'roduct contained in commercial 'roduct can 5e minimi@ed 5y a''ro'riate design and o'eration. 1//ecting more com'lete se'aration /or materials 0ith 5oiling 'oints that are not so 0idely se'arated as2 /or e"am'le2 those o/ *inyl chloride and the *arious lo0er molecular 0eight side 'roducts is /or the most 'art a matter o/ correct design and construction and o'eration cost. i//erences in concentration o/ residual 5y-'roduct POPs in commercial 'roduct may 5e due to di//erences in local regulation o/ 'roducts. ).1." Elimination of Carbon Electrodes for Chloral<ali Production. Older technology in the manu/acture o/ chlorine and caustic soda utili@ed gra'hite anodes. 4esidues /ound /rom cells so constructed contained signi/icant amounts o/ PC and es'ecially PC F.2 -his 'ro5lem 0as eliminated /ollo0ing the in*ention o/ the coated

-'

Section VI.F: Chemical Production Processes

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titanium anode 5y H. #. #eer in 1,&$ and su5se<uent su5stitution /or gra'hite in these 'rocesses.1$ -he use o/ gra'hite electrodes does not constitute #.-. ).1.( Elimination of Al<ali Treatment of 1?"?)?+-Tetrachloro!henol and "?)?+Trichloro!henol. %anu/acture o/ 22!2$--richloro'henol 0as accom'lished 5y al6ali treatment o/ 1222!2$-tetrachloro5en@ene. -his chlorinated 'henol2 in the 'resence o/ e"cess al6ali2 could generate signi/icant amounts o/ side-'roduct -C . -his 'rocess does not constitute #.-. ).1.) Elimination of Phenol .oute to Chloranil. -his 'rocess is descri5ed in the -ool6it.2 Chloranil :2232$2&-tetrachloro-22$-cyclohe"adiene-12!-dione; is the 'recursor /or 'roduction o/ dio"a@ine dyes. )hen 're'ared 5y chlorination o/ 'henol or aniline *ia elemental chlorine2 signi/icant amounts o/ PC =F are generated as 5y-'roducts. -his 'rocess does not constitute #.-. Chlorination o/ hydro<uinone 5y HCl generates much cleaner 'roduct. ).1.+ *odified Production of Pentachloro!henol (PCP) and #odium Pentachloro!henate. -he /ollo0ing 'rocesses are also descri5ed in the -ool6it. 2 -hree routes to PCP are 6no0n commercially. Chlorination o/ 'henol 5y Cl 2 o*er a catalyst2 hydrolysis o/ he"achloro5en@ene :HC#; 0ith sodium hydro"ide and thermolysis o/ HC#. -he most common route today is the /irst. Sodium 'entachloro'henate can 5e 'roduced *ia hydrolysis o/ HC#2 or more commonly2 5y treatment o/ PCP 5y sodium hydro"ide. For 5oth 'roducts2 care/ul control o/ reaction conditions :e.g.2 tem'erature2 chlorine /eed rate and 'urity o/ catalyst; leads to signi/icant reductions o/ dio"in microcontaminants. In the 8S2 emission o/ these materials 0as reduced /rom ca 3-! mg I--1B=6g in the mid- to late-1,+As to ca 1 mg I--1B=6g in the years since 1,++. 3 Facilities utili@ing 'roducts manu/actured in the 'rocesses named a5o*e should also e"amine the need /or secondary measures o/ their o0n2 es'ecially #.- 0aste dis'osal 'ractices. )." Primar% *easures of @esser /m!act ).".1 $se of 3%dro'en in &4%chlorination. O"ychlorination 'rocess /eed 'urity can contri5ute to 5y-'roduct /ormation2 although the 'ro5lem usually is only 0ith the lo0 le*els o/ acetylene 0hich are normally 'resent in HCl /rom the 1 C crac6ing 'rocess. .cetylene /ed to the o"ychlorination reactor could 5e con*erted to highly chlorinated C 2 'roducts2 and chlorinated C2 'roducts can gi*e rise to chlorinated aromatics *ia cyclotrimeri@ation.1121& Selecti*e hydrogenation o/ this acetylene to ethylene and ethane in a reactor 'rior to the o"ychlorination reaction is 0idely used as a 're*enti*e measure :See Figure 2;

-(

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

)."." Catal%st *aintenance and Tem!erature $niformit% Control. Fluidi@ed-5ed reactors tend to ha*e 5etter tem'erature control2 and more uni/orm 'er/ormance2 although the 're*iously mentioned attrition o/ catalyst 'articles can allo0 /or carryo*er into other streams 0ithin the /acility. For /i"ed-5ed o"ychlorination catalysts a''ro'riate 'ac6ing and maintenance can reduce hot s'ots and 'otentially can 5oth reduce /ouling o/ the catalyst 5ed2 loss o/ 'roducti*ity and the 'otential /or generation o/ high molecular 0eight 'roducts. Catalyst 5eds are changed on a regular 5asis to maintain e//iciency. ).".( .eduction in Aromatic 3%drocarbons in 0eeds to &4%chlorination Processes. -0o 'atents s'eci/y 'retreatment o/ air1( or HCl1+ reagents used in o"ychlorination to remo*e aromatics2 'resuma5ly 'recursors to *arious POPs. -his technology2 5eing 'atented2 is 'ro'rietary and as such is 'ro5a5ly not a''ro'riate /or #.- 5ut indicates another 'rimary a''roach. ).( #econdar% *easures ).(.1 BAT for ;aste is!osal Practices. Since all or nearly all POPs 5y-'roducts are isolated in the 5y-'roduct stream2 'ractice o/ #.- in destruction o/ these 5y'roducts2 including the com5ustion ste'2 is critical /or POPs minimi@ation. Com5ustion technology has 5een de*elo'ed that discriminates against generation o/ POPs. In addition to 're*ention o/ /ormation2 treatment o/ gases 'rior to release reduces emissions o/ POPs. 0i'ure -. #chematic of o2nstream Treatment of Combustion Products.

In the 8S2 1uro'e and Ka'an there are s'eci/ied technologies /or treatment o/ /lue gas2 0aste 0ater and 0aste solids /rom com5ustion 'rocesses. For /lue gas they in*ol*e2 among others2 ra'id cooling or neutrali@ation2 addition o/ acti*ated car5on and remo*al o/ solids *ia 'ro'erly designed 5aghouses or electrostatic 'reci'itators. For 0aste 0ater2 they in*ol*e2 among other 'rocesses2 neutrali@ation2 settling 'onds and 5iological treatment. )aste solids may 5e de'osited in a secure land/ill or in some cases used as /iller in 'roducts such as as'halt or concrete. e*elo'ment o/ #41Fs 5y the 18 or #.- under the Stoc6holm Con*ention on Ha@ardous )aste Com5ustion and do0nstream treatment o/ gas2 li<uid and solid -)

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

0astes 0ill 5e use/ul here as the 'rocesses are /airly 0ell-6no0n and generic. )hen these techni<ues are 'racticed2 emission o/ 5y-'roduct POPs is *irtually eliminated. +.0 #ummar% of *easures. %odi/y 'rocesses to reduce generation o/ 5y-'roduct POPs. Incor'orate ste's that treat im'urities in ra0 materials2 and use rigorous o'erational maintenance. Puri/y 'roducts 5y distillation. Internally recycle inad*ertently generated high molecular 0eight side-'roducts as an integral 'art o/ the 'rocess. ,.0 Performance #tandards. Per/ormance standards can 5e set locally in indi*idual 'lant 'ermits2 and 0ill *ary. #y-'roduct PC =F emission is mentioned in the 1CV% Charter2 and re/lected in the OSP.4 'rocess *ia ecision ,+=! and ado'tion o/ #.- *ia P.4CO% 4ecommendation ,&=2. -hat standard is 1 Ng -1B=ton o"ychlorination ca'acity release to 0ater. .ir emission limits in the 1CV% Charter are A.1 ng -1B=Hm.3.1, -his limit corres'onds to the 18 regulatory limit /or emissions o/ PC =F to air /rom incinerators. 7imits in other regions=countries 0ill ty'ically 5e congruent 0ith ha@ardous 0aste com5ustor regulations in local areas. -.0 Performance *easures. -hese may include: analytical chemistry on emission streams> in some areas2 re'orting o/ POPs to a Pollutant 4elease and -rans/er 4egistry :P4-4;2 such as the -o"ics 4elease In*entory in the 8S. 2A221

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Section VI.F: Chemical Production Processes

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A!!endi4 A: #%nthesis of commodit% chemicals Chemical Chlorine2 Caustic soda Process HaCl O H2OPPD Cl2 O HaOH O H2 See 1IPPC# #41F2 1"'ert 3rou' 'resentation Process $se %ore Common Co-Products

&r'anics .llyl chloride

irect chlorination o/ 'ro'ylene D3AA deg C> Pyrolysis o/ 122-dichloro'ro'ane

%ore Common 7ess Common 7ess Common %ore Common

HCl Chlorinated ole/ins2 HCl

Chloranil dye See tool6it Chloro'rene :2C2H2 O CuCl=HH!ClPPD*inyl chloro-123-5utadiene; acetylene O HClPPD chloro'rene Va'or 'hase #utadiene O Cl2 PPD 12! Q 32! dichloro> isomeri@ed :Cu catalyst; to 32! dichloro> -HCl *ia HaOH> distilled to se'arate lo0 5oiling mono-Cls> 32!-di> 12!-di> hea*ies Chlorinated 5en@enes Va'or 'hase: #en@ene O Chlorine O HCl 7i<uid 'hase: Cl2=FeCl3 to yield mi"> controlled 5y amount o/ chlorinating agent :monos; some other s'eciali@ed 'rocesses /or certain isomers> high Cl materials can 'reci'itate. Puri/ied 5y distillation and crystalli@ation> se'arations di//icult.

HaCl> o*erchlorinated 'roducts

7ess Common %ore Common

%i"ed 'roduct HCl

-+

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

1'ichlorohydrin

.llyl chloride O HOCl :chlorine %ore 0ater; PPD glycerol chlorohydrins O Common HaOH=:CaOH;2PPDe'ichlorohydrin>

Hydroly@ed 'roduct> 'olymers

Steam stri''ed then distilled. .lso: 'ro'ylene OO22 :Pd catalyst; PPD allyl acetatePPDallyl alcohol O Cl2 PPD allyl chloride Isocyanurate disin/ectants Phosgene Isocyanuric acid O HaOH O Cl2 CO O Cl2 used *irtually immediately to 'roduce 'olycar5onate and 'olyurethane 7esser chlorinated Phenols: 'henol %ore O Cl2> *arious 7e0is acid catalysts: Common FeCl3 2 InCl2 'henol O Cl2> .lCl3 as main industrial catalyst>1AA-1+A deg C> He"achloro5en@ene :HC#;OHaOH Sodium Pentachloro'henate PCP O HaOH HC#OHaOH Vinylidene Chloride :ViCl2; 12122-trichloroethane O HaOH or Ca:OH;2 > can also 5e a co'roduct o/ high tem'erature chlorination o/ C2 materials. %ore Common 7ess Common %ore Common 7ess Common %ore Common HCl HaCl HaCl HaCl HaCl or CaCl2

Chlorinated Phenols

Pentachloro'henol :PCP;

-,

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

Vinyl Chloride :VC%;

.cetylene O HClPPD*inyl chloride> Hg catalyst 1thylene O Cl2 PPD1 C :direct> Fe catalyst;> HCl O O2 O 1thylenePPD 1 C :o"ychlor> Cu catalyst;

7ess Common %ore Common

See 18 #41F2 1"'ert 3rou' Presentation C1 Products %ethyl Chloride CH! O Cl2 *ia heat or light CH3OH O HCl PPD CH3Cl %ore Common %ore Common %ore Common 7ess Common

Other Chlorinated %ethanes

CH3Cl O Cl2 heat or light PPD CH2Cl22 CHCl32 CCl! CS2 O Cl2PPDS2Cl2 O CCl! CS2 O S2Cl2 PPD S O CCl!

C" Products Chlorinated Ethanes 121- i VC O HCl=FeCl3

%ore Common

122- i :1 C;

1thylene O Cl2 PPD 1 C :Fe cat; %ore :direct chlorination; Common 1thylene O HCl O O2 :Cu cat; PPD1 C :o"ychlorination; 121- i O Cl2 :Photochemical; 12122--ri PPDPPD12121--ri 1thane O Cl2

12121--ri

%ore Common %ore Common 7ess Common

HCl

%.

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

12122--ri

VC O Cl2 1 C O Cl2

%ore Common %ore Common %ore Common %ore Common

HCl HCl

1212122--etra2 1212222-etra

1 C O Cl2 :can include o"ychlor; C2H2 O Cl2 C2H! O Cl2

HCl

121212222-Penta

-C1 O Cl2PPDPenta

Chlorinated Eth%lenes -richloroethylene :-C1; and Perchloroethylene :PC1; 1 C O Cl2 PPD -C1 O PC1 1 C O Cl2 PPD PC1 OCCl! 2 CCl! PPD PC1 1 C OCl2 OO2PPD PC1=-C1 -etrachloroethanes O HeatPPD -C1 Pentachloroethane O HeatPPDPC1 /nor'anics HCl %ore Common %ore Common %ore Common %ore Common %ore Common 7ess Common HCl HCl

HCl HCl

-iO2

#y'roduct> salt Osul/uric acid> hydrogen Ochlorine> 4eco*ery /rom com5ustion o/ chlorinated organics C2 Cl22 -iO2 OrePPD -iCl! O O2 PPD -iO2 -iO2 Ore O H2SO!PPD-i:SO!;2PPD -iO2 Iron or iron o"ide O HClPPD FeCl3 Ha: 2HaOH O Cl2 PPDHaOCl

%ore Common %ore Common 7ess Common Cl22 recycle sul/ates

FeCl3 Hy'ochlorites

HaCl

%-

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

Ca: Ca:OH;2 O2Cl2 PPDCa:OCl;2 also *ia HaOCl used as aid in chloride remo*al> reco*ered2 then dried

CaCl2

InCl2 ClO2

In O HClPPD InCl2 3enerated /rom HClO2 or HaClO3

%%

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

.''endi" #: Chlorine Product -ree2 ada'ted /rom )orld Chlorine Council Sustaina5le e*elo'ment 4e'ort :chlorinetree.'d/2 a''ended;

%&

Section VI.F: Chemical Production Processes

DRAFT 13/04/04

.E0E.EACE#

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