# OAR Box 1867

Prepped by Ollie Stewart



## Document

Number: 

# 9 ) ll-B-6 3 Docket Number: 

# A-90-1 9

Printed 12/2/20086:27:19AM Sheet 9of 95 p. 1P. 2 

# A-90-1 9 I I B 6 3

MEMORANDU M TO : FROM : DATE : SUBJECT : Proces s Vent s Docke t A-90-1 9

Wand a Floy

d Decembe r 199 0 i HONNESHAP : Industr yCharacteristics/FormaldjhyBP AAI R DQCK E ••— •TM"iini i n i n M 

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### Attache d i s a product-proces s summar y(PPS ) fo r the productio n o f Formaldehyd e vi a Dehydrogenatio n o f Methano l an d Formaldehyd e vi a Ai r Oxidatio n o f Methano l category . Thi s PP S wa s develope d a s par t o f the Industria l Profil e projec t i n suppor t o f the Hazardou s Organi c NESHA P (HON ) regulatoryeffort . Informatio n i n thi s PP S i s use d a s a basi s fo r emission s an d cos t impac t estimate s fo r the HONprogram . Liste d belo w ar e th e ke yreference s use d i n developin g the attache d PPS . "Formaldehyde. " In : Chemica l Marketin g Reporter . Schnel l Publishin g Company , Inc. , Ne w York , Septembe r 18 , 1989 . 198 9 Directoryo f Chemica l Producer s USA . SR I International , California . p . 671 . "Formaldehyde. " In : Mannsvill e Chemica l Products . Ne w York , Jun e 1983 . White , Howard . Introductio n t o Industria l Chemistry . John Wile y& Sons , Ne w York . pp . 106-107 . EPA-450/3-80-028d . Organi c Chemica l Manufacturing . Volum e 9 : Selecte d Processes . Decembe r 1980 . Weissermel , Klau s an d Arpe , Hans-Jurgen . Industria l Organi c Chemistry . Verla g Chemie , Ne w York , 1978 . pp . 34-37 . Chenier , Philip , Jr . Surve yo f Industria l Chemistry . John Wile y& Sons , Ne w York , 1986 . pp . 208-209 . Shreve , R . Norri s an d Brink , Jr. , Josep h A . Chemica l Proces s Industries . 4t h edition . McGraw-Hil l Boo k Company , Ne w York , 1977 . p . 598 . 

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pormaldehyd e (Formi c aldehyde ) (Methanal ) (Methy l aldehyde ) Methylen e oxide ) (Oxomethane ) (Oxymethylene ) t fcrdenlnc. n ^Smm ^£lfc * Borde n Chemica l Divisio n u Adhesive s an d Chemical s Divisio n .jOtmopous . Alabam a % *OiScWTexas.. . 31 > • Feyettevil!e,.Nort h Carolin a 3flO j Ff«m6nt, : Galiforni a 104 - , f Kent , Washington ' ~~~ ~ L a Grande , Orego n Louisville , Kentuck

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13 5

Source : SR I Internationa l estimate s a s o f Januar y 1 , 1989 . 

### 14* 5 Formaldehyde-sodiu m bisulfit e adduc t (See: Sodiu m formaldehyd e bisulfite ) Formamidin e disulfid e dihydrochlorid e Fran k Enterprises , Inc . Columbus , Ohi o

SR I Internationa l 67 1P. 8



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SR I Internationa l 67 1P.2 7



### PRODUCT-PROCES S SPECIFI C INFORMATIO N 

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## P^ e number s throughoutwritte n

Aportio n o f th e ai r i s passe d throug h th e vaporize r column , wher e i t i s saturate d wit h methano l (Strea m2) . Th e methanol-saturate d ai r i s the n mixe d wit h th e regain

in g ai r an d preheate d b yhea t exchang e wit h th e produc t ga s leavin g th e converter . Th e fee d ga s mixtur e (Strea m3 ) the n enter s th e converter . Conversio n ratio s o f 97 % ar e obtained . Th e converter , heate d byth e exothermi c oxidatio n reaction , i s **>- 0 maintaine d a t 345° C (ref . 5 ) b yboilin g hea t transfe r flui d i n th e reacto r shell . Stea mi s generate d bycondensatio n o f th e heat-transfe r flui d vapors . Th e produc t ga s (Strea m4 ) i s coole d b yhea t exchang e wit h th e fee d ga s mixtur e and the n quenche d i n th e absorbe r column . Th e formaldehyd e and methano l ar e re move d fro

mth e ga s strea

mb yabsorptio n i n th e aqueou s solution . Th e unabsorbe d gase s and vapor s exi t a t th e to p o f th e absorbe r column . Aportio n (6 0 t o 80% ) o f thi s ga s i s recycle d (Strea m5 ) an d th e remainin g ga s i s vented . Th e produc tP.3 0



### solutio n draw n fro m th e botto m o f th e absorbe r colum

n contain s approximatel y 0.8 % Mthano l an

d 0.005 % formi c acid . The solutio n i s usuall y

treate d i n an ion exchang e syste m t o 'reduc

e th e acidity

an d i s the

n stored . A s a fina l ste p wate r i s added t o provid

e a suitabl e concentratio n for storage an

d shipping . Proces s yield s o f

1, 5 9 1 t o 93 % are reporte

d for th

e metal-oxide-catalys t process . Th e formaldehyde yiel d fro m th e metal-oxide-catalys t proces s i s highe r tha n tha t fro m th e metallic-silver-catalys t proces s an d th e metal-oxide-catalys t proces s i s simpler , becaus e methano l distillation i s no t required . Th e equipmen t cost s fo r th e metal-oxide-catalys t proces s ar e greate r becaus e o f th e large volum

e ga s streams ; also , becaus e o f a lowe r concentratio n o f formaldehyde in th e produc t ga s stream , th

e absorbe r colum

n diamete r i s large r an d th e operatin

g temperatur e i s lower tha

n thos e used wit hth e metallic-silver-catalys t process .



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# 1AI i

METHAtJOl . STORAG E
CAUSTI C WATE R

AI R

@ - STORAG E EMISSION S ? ) - WAUDUV4G , EMI^blOU S tj ) - FUGITIV E EMlVblOW S -

OVERAU L PI.AU T ® - SECOWDAR- f EMISbtO U POTEW T I u »

PRODUC T STORAG E

^ PRODUC T ( W-Ci")

FRACTIOUATIO M 

### Fig . III-l . Flo w Diagra m fo rUncontrolle d Mode l Plan tProducin g Formaldehyd e fro m

Methano l wit h th e Metallic-Silver-Catalys tProces sP.4 2 

# SH-3? 7
fourth edition 

# CHEMICA

L PROCES S INDUSTRIE S

R . MORRI S SHREV E Lata Prof—orEmaritmt of ChomUeaJ

EagimaaHng Purdaa Lnivtnily 

### JOSEP H A . BRINK , JR . Conutldng OumUmi Eagim—r Prof—orand

Chairman of

Ckamicmi Engimaarlng faMngtom Stmto VnimnHy

NcCRAW-HIU . BOO KCOMPANY Sam I M * . IM * Sam flmli n Aaama

.VavlM U Panama ST*—f Taara Tm rarlt

Saaramm 

# RADIAN LIBRARY DURHAM , N. aUmnrwot Cttaiogtagfa i Dat a Shrew , Rudolp h Norris . 188S-1975 . Chemica l proces s industries . Include s bibliographie s to d index . 1 . ttemistry. Technical . I . Brink . Joeeph A. , date , join ttudior . II . Tide. . TP145.S 5 197 7 660. 2 77-423 6 ISB N 0-07-057145- 7

Copyright© 1977 . 1967 , 195 6 by McCrtw-Hill , Inc . Al l rights Copyright194 5 by McCftw-Hill , In c Al l rights reserved . Printe d i n th e Unite d State s o f America . N o par

to f thi s publicatio n ma

y b e reproduced , store d i n s retrieval system , o rtransmitted , i n an

y for m o rby any means , electroni c mechanical , photocopying , recording , o rotherwise , widnu t. di e prio rwritte n permissio n o f di e publisher . 3456789 0 FGRFG R786543210 9

Tha editon forOOM

book won Jeremy Robinson and EitherGettm, and the production supervisorwo tfoss aF. Leaden. It wot set in Bodomi Book. Printed and bound by Fairftetd

Graphics.P.4 4

>\Ave . • \ U 4 < 

# .,.1 - 59 8 [Chap. 34) Plastic Industries Dilute caustic. 

# LS I Ai r

_scrubber tir —Q— *\\ Ottgoses Preheote r
y Compresso rSteam Filte r

/""* \ Methanol S'Or t jrlrLj—f* 

# (ra ) Supemeote

r *^teom 

# A

>

Converte r Primor

y . i I I absorbe r

W
Vaporize r Steam +&• Steam condensate Secondar y absorbe r 

### info ft3f V ' 

# rt z ^ flMoke n

U tan k \J 

### L 

# sr ^ Recycle methanol Fig. 34.8 Flowchar tto rth e manufactur e ot' formaldehyde .
I f two molecule s of

aci d react , acompoun d suc h a s ethyliden e diacetat e i s formed :
Th e newe rmethod , however , i s to startwit h ethylen e and by oxychlorinatio n (dehydrochlorination i obtai n apparentl y acheape rprocedur e for. linv l chloride.** Se e Fig . 34.9 . whic h presents aHowcha

forth e followin g reactions : Chlorination CjH 4 + Q 2 —-»QH^ j

DichloroethyleQ

e Oxychlorination CjH , + J0 2 + 2H Q -^ » CjH 4 a 2 + H 2 0 Dehydrochlorination

cricking furnace. 

### c*HA "^ a 

### ~-< C 2H 3 Q 

### + H Q

ta d pretiu n Dichloroethyleii

e Viny l chlorid e Th e CuQ 2 catalys t(o n a n inertfixe d carrier ) ma y reac ta s follows : CjH 4 4- 2CuO

j • CjH ^ + Cu-jCl

j CujCl j + JO , • Cu

O • Cud j Cu O • CuQ j + 2H Q • 2CuQ 2 + H 2 0

4> Edward aan d Weaver . Ne w Rout e t o Viny l Chloride. Chem. Eng. Prog.. 61(1) . 2 1 (1965 ) (prescribe d cost s relativ e t o proces s startin g with ethylene) ; Burk e an d Miller . Oxychlorination , Chem. Week, Aug . 22 . 1964 . p . 9 3 (excellen toveral l commercial an d technica l presentatio n an d patents) ; Riege l et at.. Lo w Cos tHydrocarbo n Chlorination . Chtm. Eng. Prog.. 69(10) . 8 9 (1973) . /

C'ONV E OC E :

OXYCHLORIN ' 'fig. 34.9 F !

HC I . = 7312-H . 10 2 •
PHTH , th e establis l man y plast

i mines , eryt

l facturin aa

r (Chap . 39) . abl e prices , expande d t ; plasticizer s Th e p t thalen e wh

t t o carbo n d in g phthalii Btu/l b of

r

Oxide agent i s ai l
"ECT . ; "Phthal i Eng. (.V . Y.). :P.4 5



# Surve y o f Industria l Chemistr y

Phili p J . Chenie r Professo r Departmen t

o f Chemistr y Universit y o f

Wisconsin-Ea u Clair e Ea u Claire , Wisconsi n

A Wiley-Interscienc e Publicatio n JOH N WILE

Y & SON S Ne w Yor k • Chicheste r• Brisban e Toront o • Singapor eP.4 6

-vi - ' 20 8 Chemicals

from Methane 

## 0 I I Formaldehyde , H-C-H ; Methana l Reference s I . & M . pp . 422-42 9 CP
. 9-26-8 3 KC
. 2-4-8 5 Formaldehyd e i s produce dsolel y fro mmethanol
. Th e proces s ca n b e ai r oxidatio n o r

simpl e dehydrogenation
. Variou s meta l oxide s ar e use da s catalysts
. Temperature s rang e fro m450-90()° C an dashor t contac t tim e o f 0.0 1 sec . Formaldehyd e i s stabl e onl y i n wate r solution , commonl v 37-5fic j formaldehyd e b y weight
. Methano l (3-15% ) ma y b e presen t a s astabilizer
. Formaldehyd e i n th e pur e for mi s aga s wit h ab p o f -21° C bu t

i s unstabl e an dreadil y trimerize s t o trioxan e o r polymerize s t o paraformaldehyde
. oxidatio n 2CH 3 O H + 0 2 — dehydrogenatio n CH 3 O H A» a- CH 2 = O + 2H_> 0 CH o = O + H o 

# r-i
trioxan e H0-(CH 2 -0)- H n n = 8-5 0 paraformaldehyd e
Use s o f Formaldehyd e Urea-formaldehvcl e resin s Phenol-formaldehvd e resin s Pentaervthrito l Hexameihvlenetetramin e (HMTA ) Urea-formaldehvd e concentratio n Polvacetal s 1.4-butanedio l Melamine-formaldehyd e resin s MD I 25<7 C 2 0 7 7 6 5 5 4 4 Tw o importan t

thermosettin g plastics , urea - an dphenol-copolymers , tak e nearl y on e hal f

th e formaldehyd e manufactured
. 1,4-Butanedio l is mad e fo r som e polyester s an di s a n exampl e o f acetylen e chemistr y tha t ha s no t ye t bee n replaced
. pentaeryt h tetranitrat t t ondensa t \tetalcleh \ coiidensuti ' (ormaldef r

O I I C H 3 - C

-

Hexame t noli c resi n i Althoug h it condensati o

Debat e i s products , e constructio n TL V o f fo r irritan t an d Consume r

P insulation , iv T h e fina l si carcinogen. "

### >n>ces s ca n b e ai r \ide s ar e use da s u t contac t tim e o f
• mmonl v M-ji') c/



### r en t a s astabilizer
. ' C bu t i s unstabl e iformaklehyde
. + 2H 2 

### 0 H- ,

nol-copolymers
. i .4-Butanedio l i s hemistr v tha t

ha s Methanol. CH 3 OH; Wood Alcohol. Methyl

Alcohol 20 9 

### HC^C H + 2CH, 0 HO-CH,-C=C-CHo-O H 2H , 

### *
. HO-CH 2 

### -CHo-CH 2 

### -CH 2 

### -O H Pentaervthrito l finds end-use s i n polyester s an dexplosive s (pentaervthrito l tetranitrate)
. T o appreciat e thi s synthesis , th e studen t shoul dreview tw o condensatio n reactions , th e crosse daldo l an dth e crosse dCanizzarro
. Acetaldehvd e react s wit h 3 mol o f

formaldehyd e i

n thre e successiv e aldo l condensations
. Thi s produc t the n undergoe s aCanizzarr o reactio n wit h formaldehyde
. O I I CH3-C- H + 3CHo O O H 

### O H I CH o o -s - HO-CH 2 

### -C-C- H -£££
.

| OH " 

### CH 2 

### I O H C(CH 2 

### OH) 4 

### + HCOO H pentaerythrito l Hexamethylenetetramin e (HMTA ) ha s importan t use s i n modifyin g phe

noli c resi n manufactur e an di s a n intermediat e i n explosiv e manufacture
. Althoug hi t

i s acomple x three-dimensiona l structure , i t i s easil y mad e b y th e condensatio n o f

formaldehyd e an dammonia
.
CH 2 0 A

### mj 

### ,N h 6 H2 O Debat e i s continuin g o n th e safet y an dtoxicit y o f formaldehyd e an dit s products , especiall y urea-formaldehyd e foa muse da s insulatio n i n constructio n an dphenol-formaldehyd e a s aplywoo dadhesive
. Presentl y th e TL V o f formaldehyd e i s 2
. Conflictin g studie s o f formaldehyd e a s a n irritan t an dpossibl e carcinoge n aboun di n th e literature
. Althoug hth e Consume r

Produc t Safet y Commissio n banne dure aformaldehyd e foa m insulation , i n 198 3 aU.S
. Circui t Cour t o f Appeal s overturne dthi s decision
. Th e final stor y i s stil l t o b e written
. Formaldehyd e i s no w a"suspec t carcinogen. "

# Klau s Weisserme l Hans-Jiirge

n Arp e 

# Industria l Organic Chemistr

y Importan

t Ra w Material s and Intermediate s Translate db

y Alexander

Mullen



# Verla g Chemi e • Weinhei

m• Ne w Yor k 197 8P.4 9

Prof
. Dr . Klau s Weissermel Dr . Hans-Jiirge n Arp e Hoechs t AG Postfach 80032 0 D-623 0 Frankfur

t 8 0 West Germany 

# Prefac e

Cop y Editing : Dr . Han s F . Ebel Thi s book contain s 4 3 Table s CIP-Kurztitelaufnahm e der Deuischen Bibliothek Weissermel
. Klau s Industrial organi c chemistry : important ra w material s andintermediates' / Klau s Weissermel ; Hans-Jiirge n Arpe
. - l.Aufl
. - Weinheim , New York : Verlag Chemie , 1978
. Dt . Ausg
. u.d.T. : Weissermel
. Klaus : Industriell e organisch e Chemie
. ISB N 3-527-25706- 3 (Weinheim) ISB N 0-89573-005- 7 (Ne w York ) NE : Arpe , Hans-Jiirgen : © Verlag Chemi e GmbH , D-694 0 Weinheim , 197 8 Al l right s reserve d(includin g thos e o f translatio n int o foreign languages)
. N o par t o f thi s boo k ma y b e reproduce di

n an y for m- b y photoprint , microfilm , o r an y othe r mean s - no r

transmitte dor

translate dint o amachine languag e without writte n permissio n fro

mthe publishers
. Registere dnames , trademarks , etc . usedi n thi s book , even withou t

specific indicatio n thereof , are no t t o b e considere d unprotecte db

y law
. Printer : Passavi aDruckere i GmbH Passa u Printe di n West German y Industria l organi c c r a s wel l as , t o a n inc i presen t statu s of

k n Ther e wa s thu s agr

< an dintermediate s c an dt o presen t

i t i n i development , whic h fro mthei r

industria l in g discussion s wit h Thi s boo k

address e fro mi t th e chemist i manufacturin g pro c glea n informatio n a an dfeedstock s alo r discipline s i

n th e cl economist s - wil l b economi c interrela t Thi s boo k

i s arran g thei r tightes t possi t unavoidable
. Th e i

i A s arule , th e man u men t an dsignifica ; application s of

th e r product s ar e frequ * existin g technologi c mor e economi c o r

i Th e author s endea * informatio n ar e a t

• 1
. Th e mai n text . 2
. Th e synopsi s of

I 3
. Flo w diagram s i

l Thes e thre e type s o o r makin g brie f

n o note s whic hbriefl y t o b e rapidl y infor r

### \r>-h3 4 2. Basic Products of Industrial

Syntheses

Hoechsl-Uhd e Mitsubishi Ga s Chemical Shell a t plannin g stage : Dor Chemicals
. Israe l feed , othe r companie s suc

ha s Hoechst-Uhde , Shell , Mitsubish i Ga s Chemica

l andDor Chemical s i

n Israe l eithe r

operat e or

ar e plannin g pilot

plant s wit

h methano l a s substrate
. I n b e

commercial form s o

f HCHO :

1
. hydrate , HCH O H : 0 HO-CH,-O H H-K>CH 2 ^O H > i < 10 tnoxa n Cf^ o 3
. paraformaldehyd e H-f-OCH,-r;OH "

' M > 1 0

HCH O feedstocks : 1
. CHjO K

approx . 92 % shar e 2
. C,-C i alkanes , approx . 8% shar e 3
. (CHJOCHJ )

HCH O productio n (in

197 4 US A 0.9 8 W . German y 0.5 0 Japa n 0.3 7 millio n t) : 197 5 0.7 7 0.4 0 0.3 1 197 6 0.6 9 0.4 9 0.3 8 HCH O manufactur e fromCH 3 O H accord

ing t o tw o principles : I dehydrogenatio n o r

oxydehydrogenatio n wit hAg o r C u 2
. oxidatio n wit

hMoO j + Fe ; 0 3 characteristi c difference s becaus e o f explo

sio n rang e fo

r CH,OH/ai r

betwee n 2.3.2 . Formaldehyd e A t roomtemperature , formaldehyde is acolorles s ga s whic h readily polymerize s i

n th e presenc e o

f minute amount s o

f im

purities
. Therefore , there are thre e commercia l forms usuall

y availabl e i n plac e o f th e monomer : l.Th e aqueou s 35-55 % solutio n i n whic hformaldehyde is present to ove r 99 % as th e hydrate or

a s amixtur

e o f oxy methylen e glyco

l oligomers
. 2
. The cyclic trimeri c for

mcalle dtrioxa

n obtaine dfro

mth e acid catalyze dreactio n o

f formaldehyde
. 3
. Th e polyme

r for mo f formaldehyde calle dparaformaldehyd e whic h result s fro

mth e evaporatio n o

f aqueou s formaldehyde solutio n andwhic

h ca n b e reversibly converte dto the mono me r b y th e actio n o

f hea t or acid
. The processe s fo

r manufacturin g formaldehyde are base des sentially on methanol.an dth e ligh t hydrocarbon s (methan e to butane ) a s feedstocks
. Methano l ha s develope dfro mth e first

commercially operate d dehydrogenatio n i

n 1888 , to th e currentl y dominatin g sourc e o f formaldehyde
. Only_in

_th e USA , asmal

l amount o f forma): , dehyd e (approx
. 8 % o

f worldproduction ) is manufactured , via radica l oxidatio n o

f ligh t hydrocarbons
. Beside s these , the oxidatio n o

f dimethy l ethe r

is als o o f som e importance
. Th e availabl e productio n figure s fo r formaldehyde i

n severa l importan t industrial countrie s are liste di n th e adjacent

table
. 2.3.2.1 . Formaldehyd

e fro m Methano

l Formaldehyd e ca

n b e manufacture dfro

mmethano l via tw o basically differen

t reactio n routes : 1
. Dehydrogenatio n or

oxidativ e dehydrogenatio n i n th e pre senc e o f A g o r Cu catalysts
. 2
. Oxidatio n i

n th e presenc e o

f Fe-containin g Mo0 3 catalysts
. Th e oxidativ e dehydrogenatio n proces s wit hA g o r C u meta l i s operate dabov e th e explosio n limit wit h asmall quantit

y o f air
. . A d l l t l V' a I•\A » 

# A 2.3. C,-Units '3 5 P.5 1

e . Shell , Mitsubish

i ither operat e or

are :rate .

olorles s gas whic

h it e amount s o

f im

rcia l form s usually 1 formaldehyde is amixtur e o f oxv - | n the oxidatio n process , asmall amount o f methano l is reacte d helow the explosio n limi

t wit h alarg e exces s o

f air
.

To I: A acatalyst s (crystal s or

nets ) are preferentiall y employe di n th e detndrogenatio n andoxidativ e dehydrogenatio n o f methanol , [ n the BASF
. Degussa , D

u Pont , IC I andMonsanto processe s the catalys t

is arrange da s afe

w centimete r

thick laye r i n th e reactor . I n th e CdFChimi e process , silve r i s use dtogethe r

wit h acarborundu msupport . I n th e initia

l step methano l is dehydrogenated : to I: small amoun t

o f 0 : . i.e. CH 3 O H conten t >36. 5 vol.-*/ : to 2: 0 ; excess , i.e. CH 3 O H conten t <6. 7 vo\.- r > 1
. HCH O manufactur e w'aCHjO H dehyd

rogenatio n o r

oxydehydrogenatio n catalys t mainly employe di

n thre e forms : 1
. 0.5- 3 m

mcrystal s 2 . net s 3 . impregnate d o n Si C linedfro mthe acid paraformaldehyd e ou s formaldehyde .•rte dto the mono ivd e are base des - 'bon s (methan e to nercially operate d minatin g sourc e o

f mount o f formal

manufacture dvia beside s these , th e mportance . dehyd e i n severa l i e adjacent

table
.

lethano l via tw o natio n i n the pre g Mo0 3 catalysts
. AgorC u meta

l is al l quantity o

f air
. CHjOH ^ HCH O + H

2 UH •• 2 0 kcal , . > + 84 U /mo 1 (15 ) Hydrogen ca

n be combuste dexothermall y on additio n o f ai r / ALI - 5 8 kca l Thu s th e followin

g forma l equatio n result s fo

r th e oxidativ e dehydrogenation : mol l

CH3O H + 0.5O 2 - HCH

O + H 2 0

' *\H 3

8 kca l 159 U /mo l (16

) A les s tha n stoichiometrical amount o f air is employe di

n th e industrial process . Th e ai

r is fe ds o tha t th e reactio n tempera ture remain s constant

(±5°C ) i n th e rang e 600-720°C
. How
ever , a t temperature s betwee n approx . 600-650° C ther e is a n incomplete methano l conversio n necessitatin g arecycle
. On addin g H 2 0 a

t 680-720° C there i s almos t complete conversio n o f th e methano l i

n asingle pass . Th e water ha s anothe r

favor

abl e effec t o n th e lif e o f th e Ag catalys t

in that th e stea mdelay s th e deactivatio n cause db

y sinterin g o

f th e thi n laye

r o f silve r crystal s durin g th e wea

k re dheat
. Th e catalys t

ha s alif e tim e o f 2- 4 month s an dth e spen t catalys t ca n b e easily regenerate d electrolyticall y without

los s o f Ag
. Th e catalys t

i s sensitiv e t o trace s o f othe r metal s a s wel

l a s halogen s andsulfur
. Th e ho t gase s fro mth e reactio n are ver

y quickly coole dt o approx . 150° C an dwashe di n acounterflo w wit

hH 2 0 i n severa l mechanis mo

f oxidativ e dehydrogenation : primar y dehvdrogenatio n o n metalli c A g o r C u secondary H- . combustio n wit h O

proces s characteristics : contro l o f oxidatio n via O , feed(adiabati c method ) withou t

externa l heat

supply o r re mova l a t 600-720°C
. i.e. A

g re dheat

H : 0 additio n ha s several effects : 1
. increase s CH 3 O H conversio n 2
. interfere s wit

h A g recrystallizatio n 3
. lower s th e C depositio n o n A g surface s therefore , increas e i

n lif e o f catalys t Ag reactivatio n via electrolyti c regenera tion : Ag dissolve da

t anod e an ddeposite da t cathod e therma l decompositio n o f HCH O t o C O + H 2 i s suppresse dthrough :\JJ -i"'H3 6 2. Basic Products of Industrial

Syntheses

1
. short residenc e time a

t thi n catalys t

layer 2
. rapi dcoolin g (0.1-0. 3 s ) t o I50° C

2
. HCH O manufactur e via CH 3 O H oxida

tion : catalyze db

y metal oxide s base do n Fe : O r MoO,
. possibly wit hCr,0 3 o r

Co O a s promoter s effectiv e catalyst : Fe(Mo0 4 ) 3 sensitiv e t o heat du e t o M0O 3 discharge
. Exces s Mo0 3 replenishe s losse s an davoid s dro p i

n activit y
proces s characteristic s o f th e oxidativ e HCH O manufacture : advantages : 1
. lo w temperatur e reduce s materia l problem s 2
. highe r HCH O concentratio n attainabl e directl y withou t

subsequen t

distillatio n disadvantages : great exces s o f ai r mean s highe r

investmen t an denerg y cost s compare dt o A g process , waste ga s wit

hHCH O non-combustibl e an d require s special HCH O removal treatmen t lif e tim e determine db

y mechanical stability o f th e catalys t

pellet s absorptio n stages . Th e solutio n is stabilize dtoward s polymeri

zatio n wit h aresidua

l amount o f methano l (l-2wt.-%)
. A distillatio n ca

n be connecte di

n order

- t o produc e concentrate d formaldehyde solution s (3 7 t o 4 2 wt.-%)
. Th e yieldo

f formal

dehyd e is 87.5%-an dth e selectivity * reache s 91%
. i.e. I t formaldehyde require s 1.2 2 t o f methanol
. The by-product s are C O an dCO : . Ther e is virtually no formic acidpresent . To 2: I n th e oxidatio n process , th e formaldehyde formatio n occur s practically a s apure methano l oxidatio n (eq
. 16)
. A mixtur e o f 18-1 9 wt.- % Fe,0 3 and81-8 2 wt.- % Mo0 3 is employe da s catalyst
. Unde r

carefull y controlle dconditions , i

t is converte d int o th e catalytically activ e iron(III)-molybdate
. Exces s M0O 3 i s frequently adde di n orde r t o mak e u p fo r losse s resultin g fro

mformatio n o

f molybdenumblue
. Thi s compoun d goe s t o th e cooler

en do f th e catalys t

bedan dsimultaneously lower s th e catalyti c activit y andselectivity
. Cr

- andCo-oxjde ca n b e useda s promoters . I n th e industrial process , methano l vapor , togethe r wit h alarg e exces s o f ai r at 350-450°C , i s ledover

th e catalys t

i n atubula r reactor . Th e hea

t o f reactio n i s remove db

y aliquidwhic

h surround s th e tubes
. After cooling t o 100° C the gase s fro mth e reactio n are scrubbe dwit

h H : 0 i n abubbl e column
. By adjust

in g th e amount

o f water , th e concentratio n o f th e formaldehyde solutio n ca

n b e varie dbetwee n 3 7 an d6 0 wt.-% . The methano l conversio n i s roughly 95-99 % andth e formaldehyde selectivi

t y reache s 91-94^ ; Th e by-product s are CO , CO , andformic acid
. Th e latte r ca n be remove di n acouple dion-exchanger
. Th e lif e time o f th e catalys t

i s roughly tw o years . Th e Perstorp
Reichhol d("Formox') , Hiag-Lurgi , Montecantini , SBA , IFP-CdF , an dLummu s processe s wer e develope di

n accord

anc e wit h thi s principle
. Dimethy l ethe r

is employe di

n asimila r manner t o methano l fo

r oxidatio n t o formaldehyde
. B e tr u L' U M: o f t u i o f pr . d e ti n

ut .

so l v a a n m ; \ V US ' n u F u a s 

### 7 ti c M . b u 4.

- pr .
* ) c.f. Definition s o

f Conversion , Selectivit

y an d Yield , Sectio n 15.2
.P.5 3

*J 'fir

2.3. Cr lJnits 3

7

.• dtoward s polymeri

tno l (l-2wt.-%)
. A •roduc e concentrate d Th e yieldo

f formal

- .-ache s 91%
. i.e. I t is virtually n

o formic

d e formatio n occur s ,»q . 16)
. A mixtur

e o f lo0 3 is employe da s tions
. i t i s converte d bdate
. to mak e u p fo r losse s nlue
. Thi s compoun d I andsimultaneousl y y . Cr

- andCo-oxid e togethe r wit h alarg e : catalys t i n atubula r db y aliqui dwhic

h ' C th e gase s fro

mth e e column
. Byadjust

o f the formaldehyde •vt.-% . The methano l maldehvdeselectivi

cid
. Th e latte r

ca n b e \ears
. Th e Perstorp
ontecantini
. SBA , .•velope di n accord

mer to methano l fo

r 2.3.2.2 . Formaldehyd e fro m Othe rProduct s Beside s the tw o mai

n manufacturin g route s base don methano l ihere ar e afe w les s importan t

processe s employin g othe r pre cursors . Man y companie s hav e been workin g on th e selectiv e oxidatio n o f CH 4 . However , th e lo

w rate o f reactio n o

f CH. , a t tempera ture s below 60 0 ° C couple dwit h the hig hrate o f decompositio n o f formaldehyde abov e 600° C hav e meant tha t n o industrial proces s ha s been develope dto date
. Decompositio n o f formal

dehyde coul donl

y b e avoide db

y extremel y shor

t residenc e times
. A Hiil s proces s ha s recently been describe dinvolving partial oxidatio n o

f methan e to methano l andformaldehyde
. The residenc e tim

e andpressure wer

e 1.5 5 x 10" 3 sand60bar , respectively
. I n th e Ceianes e oxidatio n proces s involving propan e or prop ane-butan e mixtures , formaldehyde andacetaldehyd e are formedi n th e gas phas e alon g wit

hnumerou s othe r

oxidatio n products
. Thi s proces s is describe di

n connectio n wit

h acetaldehyd e man ufactur e {c.f Section 7.3.2)
.
2.3.2.3 . Use s o

f Formaldehyd

e Apar t fro mth e direc t

aprjHcjitjons o

f aqueou s formaldehyde solution s (Formalin® , Forrnol® ^ e.g. a s disinfecjant_an dpreser vative
. anda s arfauxiliar

y agent i n th e textile , leather , fur
. paper andwoodindustries , most

o f th e formaldehyde is usedfo r resin manufacture wit

hphenols , ure aan dmelamine
. Water-fre e pure formaldehyde or it s trimer

(trioxan ) ca

n b e usedt o manufacture hig

h molecula

r thermoplastic s (polyoxy

methylene)
. Furthermore , th e syntheti c pathwa y t o polyhydri c alcohol s suc h a s pentaerythritoi , trimethylolpropan e andneopenty l glycol (c.f Sectio n 8.3 ) is opene du

p b y formaldehyde Waco-aldoliza

tion
. Moreover , formaldehyde is employe di n th e manufacture o

f butynedio l accordin g t o Repp e (c.f. Sectio n 4.3) , o f isopren e via 4,4-dimethyl-l,3-dioxan e (c.f. Sectio n 5.2.2) , an do f fJ

propiolacton e (c.f. Sectio n 11.1.7.1)
. HCHO manufactur e fro m ligh thydrocarbons : I.CH 4

- C 3 H S .CjHu , to I: CH 4 oxidatio n wit

h Hiils proces s (noto

n industria l scal e u p t o now) avoids HCH O decompositio n a

tth e hig h temperatur

e level necessar y b y extremel y shor

tresidence times

to 2: C 3H„.'C 4H, 0 - Ceianes e proces s fo roxida tio n use d industriall

y i n US A HCHO only i

n mixtur e wit h othe rproduc HCHO applications : 1. formaldehyde condensatio n product s (thermosettin g plastics )

2 . trioxa n fo rpolyoxymethylen e

3 . aldol reactions : pentaerythritoi , trimethylolpropane . neopentyl glycol 4 . butynediol manufacture : HOCH,CaCCH,O H 5 . various , among others : HJ C H 3 C O-' ield . Sectio n 15.2 . 

# Cf H,C-CHCOO HP.5 4


# dEFt t Unite d State s

Environmenta l Protectio n Agency Offic e o f Ai r Quality Plannin g an d Standard s Researc h Triangl e Par k N C 2771 1 

## TLS

EPA-450/3-80-028 d Decembe r198 0 Ai r 

# Organi c Chemica l Manufacturin g Volum e 9 : Selecte d ProcessesP.5 5



### 1- i


# t ' 

# V\° l REPORT 1

FORMALDEHYD

E
R . J . Lovel l
I T Enviroscienc e 904 1 Executiv

e Par k Driv e Knoxville , Tennesse e 3792 3

Prepare d fo r Emissio n Standard s an

d Engineerin

g Divisio

n Offic e o f Ai r Quality Plannin

g an d Standard s ENVIRONMENTA

L PROTECTIO

N AGENC Y ResearchTriangl e Park , NorthCarolin a

Decembe r 198 0

Thi s repor t contain s certai n informatio n whichha s been extracted fro m th e Chemica l Economic s Handbook , Stanfor d ResearchInstitute . Whereve r used , i t ha s been s

o noted . Th

e proprietar

y dat a right s whichresid e wit hStanfor

d Researc hInstitut e mus t b

e recognize

d wit han

y us e o f thi s material .


## D2 R•ta» * 

### • i a•MilJamda^lMIMBMITHIaMMMliTM 1-ii i

CONTENT S O F REPOR T 1

I . ABBREVIATION S AN D CONVERSIO N FACTOR S 

### II .

III .



### IV . INDUSTR YDESCRIPTIO N A . Reaso n fo r Selectio n B . Formaldehyd e Usag e an d Growt h C . Domesti c Producer s D . Reference s PROCES S DESCRIPTIO N A . Introductio n B . Metallic-Silver-Catalys t Proces s C . Metal-Oxide-Catalys t Proces s D . Othe r Processe s E . Reference s EMISSION S A . 

### B . Formaldehyde fro m Methano l Proces s Usin g a Metalli c Silve r Catalys t Formaldehyd e fro

m Methano l Proces s Usin g a Meta l Oxide Catalys t C . Reference s V . APPLICABL E CONTRO L SYSTEM S A . Formaldehyde fro m Methano l Proces s Usin g a Metalli c Silve r Catalys t B . Formaldehyde fro m Methano l Proces s Usin g a Meta l Oxid e Catalys t C . Reference s VI . IMPAC T ANALYSI S A . Environmenta l and Energ y Impact s B . Contro l Cos t Impac t C . References . 

### Pacr e 1- 1 II- l II- l II- l II- 3 II- 7 III- l III- l III- 2 III- 5 III- 7 III- 9 IV- 1 IV- 1
IV- 6 IV-1 2 V- l V- l
V- 5
V- 9 VI- 1 VI- 1 VI- 4 VI-2 1 VII . SUMMAR

Y VII- 1

### II- l

II . INDUSTR

Y DESCRIPTIO

N
A . REASO

NFO R SELECTIO

N Formaldehyd e productio n wa s selecte d fo r stud ybecaus e preliminaryestimate s indicated tha t emission s o f volatil e organi c compound s (VOC ) fro mthe industr

y wer e hig

h an d becaus e a n increas e i n formaldehyd e consumptio n wa s expecte d t o continue . Pure , dr

yformaldehyd e i s a colorles s ga s characterize d b ya pungen t odor . It s stabilityi n the gaseou s stat e depend s o n it s purity ; however , eve n trace s o f wate r wil l caus e rapi d polymerization . Therefor e formaldehyd e i s manufacture d an d transporte d onl yi n solutio n o r i n the polymerize d state . Th e domesti c productio n capacit yo f formaldehyd e i s reporte d traditionall yo n the basi s o f a 3 7 w t % solution , although i t i s manufacture d an d sol d i n differen t forms , e.g. , 37 , 44 , 50 , 52 , an

d 5 6 w t % solution s an d a s paraformaldehyde , a solid . Whe r eve r possibl e customer s bu yth e high-concentratio n produc t i n orde r t o reduc e freighl dehyde . 37 , 44 , 50 , 52 , an

d 5 6 w t % solution s an d a s paraformaldehyde , a solid . When
1S 1 

### freigh t charges . Appendi x Agive s the pertinen t physica l propertie s o f formal
B . FORMALDEHYD E USAG E AN D GROWT H Th e curren t productio n capacit yo f formaldehyd e i n the Unite d State s (base d o n 3 7 w t % solution ) i s 406 6 Gg/yr , wit h the 197 7 productio n bein g 275 0 Gg/yr , o r 1 2 68 % o f thi s capacity . ' Formaldehyd e consumptio n i s expecte d t o increas e a t an averag e annua l rat e o f 4 t o 5 % durin g 1977—1982 . ' A t thes e rate s productio n wil l b e 85% ; 

### p f curren t capacit yb y1982 . Th e use s o f formaldehyd e an d thei r expecte d growt h rate s ar e give n i n Tabl e II-l . Th e manufactur e o f adhesive s constitute s 60 % o f the en d us e fo r the formaldehyd e produced . Th e majo r derivative s - - urea-formaldehyd e an d phenol-formaldehyd e resin s —ar e use d principall yi n the manufactur e o f particl e boar d an d plywood . Thu s th e consumptio n patter n o f formaldehyd e depend s largel yo n the constructio n industry . The manufactur e o f plastic s account s fo r approximatel y10 % o f the formaldehyd e produced . Butanediol , a derivativ e o f formaldehyde , i s use d i n makin g polybutyl
ene terephthalat e (PBT) . I f the us e o f plasti c i n automobil e productio n increase sII- 3

and PB T plasti c i s chose n a s the principa l materia l used , formaldehyd e coul d hav e a growt hrat e o f mor e tha n 10 % annuall y fo r a fe

w years .
DOMESTI C PRODUCER S Becaus e mos t o f the formaldehyd e i s manufacture d and shippe d a s a solutio ncon tainin g 50 % o r more water , the distanc e fro m the producin g poin t t o the consumin g poin t i s minimize d t o reduc e shippin g costs . Therefor e the industr y i s charac terize d b y

a larg e numbe r o f relativel y smal l plants . Sinc e mor e tha nhal f th e formaldehyd e use d i s i n the manufacture o f adhesive s fo r woo d products , the 3 producin g plant s ar e locate d predominantl y i nthe sout han d northwest . Sixtee nproducer s were operatin g 5 5 formaldehyd e plant s a t the en d o f 1977 . Tabl e II- 2 list s th e producers , locations , capacities , an d processes ; Fig . II- l show s the plan t locations . Formaldehyd e ha s a tendenc y t o polymeriz e o nstorage . Whena ninhibito r i s adde d t o preven t excessiv e polymerizatio na t lowe r storag e temperatures , i t i s usuall y methano l a t 7 t o 11 % concentration . Mos t o f the formaldehyd e i s sol d uninhibite d an d mus t b e kep t warm (above 54°C ) t o preven t polymerization .
Al l the formaldehyd e produce d i nthe Unite d State s i s made fro m methano l eithe r b y a combinatio n oxidation-dehydrogenatio nproces s usin g a silve r catalys t o r by catalyti c oxidatio n i nthe vapo r phas e usin g a meta l oxid e catalyst . Abou t hal f th e formaldehyd e producer s als o produc e methano l feedstoc k (Borden , Ceianese , D u Pont , Georgia-Pacific , Hercules , IMC , Monsanto , and Tenneco) . Reichhol d i s the onl y larg e produce r tha t doe s no t make it s ow nmethano l feedstock .! 

### II- 4

Tabl e II-2 . Formaldehyd e Capacity
Capacity 0 

### (Gg/yr ) Locatio n Silver . Meta l Oxid e Ke y Producer Proces s Proces s

Allie d Chemica l Corporatio n I A SouthPoint , O H 14 1 4 5 3 6 10 6 11 3 3 6 5 9 10 2 3 6 2 9 4 1 10 9 ( ckk/.j d rt7t^y.ff--Hfr\ ) (

_-~t i d txkt^y^. ~)


### 2 A 2 B 2 C 2 D 2 E 2 F 2 G 2 H 21 2 J 2 K 3 A 3 B 3 C 4 A 4 B 5 A 5 B 5 C 5 D 5 E Borden , Inc .

Demopolis , A

L Diboll , T

X Fayetteville , N

C Geismar , L

A Louisville , K

Y Sheboygan , WI Fremont , C

A Kent , W A LaGrande , O

R Missoula , MT Springfield , O

R Ceianes e Chemica l Compan y Bishop , T

X Newark , N

J Rock Hill , S C Chembon d Corporatio

n Springfield , O

R Winnfield , L

A D u Pon t Compan

y Belle , W

V LaPorte , T

X Healin g Springs , N

C Linden , N

J Toledo , OH
Georgia-Pacifi c Corporatio n 

### 7 A 7 B 7 C 7 D 7E 7F 7 G 7H Albany , O R Columbus , O

H Coo s Bay , O

R Crossett , A

R Russellville , S C Taylorsville , M S Vienna , G

A Lufkin , T

X 

### 68 0

4 5 5 3

5 3 6 8 3 2

GA F Corporatio

n 6 A Calver t City , K Y4 5 5 4 45 g 

### 4l g 

### 4 5 2 7

.1 3 5 4 113 g 

### 4 5 Gul f Oi l Corporatio n 8 A Vicksburg , MS 2 7

Hercule s Inc . 9 A Louisiana , M O 7 7 9 B Wilmington , N C 4 5 Hooke r Chemical s an d Plastic s Inc . 10 A Nort hTonawanda , N Y6 1 

### riHi 22 7 14 5 10 0 7 3 i 12 2 I iP.6 0

II- 5

Tabl e II-2 . (Continued )

Locatio n Key

14 E 14 F 14 G 14 H 15 A 15 B 16 A Produce r

IM C Chemica l Group , Inc .

Moncure , N C Tacoma , W

A Tuscaloosa , A L Whit e City , OR Tennec o Inc . Fords , N

J Garfield , N

J Wrigh t Chemica l Corporatio n Reigelwood , N C Tota l proces s capacit y Numbe r o f plant s Percen t o f tota l industr y capacit y Capacit y

o f tota l industr y Capacit y (Gg/yr ) Silve r Proces s 

### 11 A 11B 12 A 12 B 12 C 12 D 13 A 14 A 14 B 14 C 14D Seiple , PA

Sterlington , L

A Monsant o Corporatio n Addyston , O H Chocolat e Bayou , T X Eugene , OR Springfield , M

A Pacifi c Resin s & Chemicals , Inc . Eugene , O

R Reichhol d Chemicals , Inc . Hampton , S C Houston , T X Kansa s City , K

A Malvern , A

R 

### 2 9 1 4 4 5 8 8 4 5 13 4 4 3 2 3 2 3


### 3 3

4 5 4 5

304 0 3 5 74. 8 Meta l Oxid e

Proces s

5 4 5 0 5 5 2 2 11 3 3 9

102 6 2 0 25. 2 406 6

a Se e refs . 1 an d 2 . Se e Fig . II- l fo r plan t locations . Becaus e o f spac e limitations , symbol s o n ma p d o no t reflec t precis e locations . Base d o n 3 7 w t % solution . Silve r catalys t process . Mixe d metal-oxide-catalys t .process . Capacit y

o f Russellville , SC , plant , whic hcame on-stream i n1975 , i s 11 3 Gg/y r [se e 197 6 Director y o f Chemica l Producers . Unite d State s o f America , p . 6 2 i n Januar y

t o Jul y

Supplement , Chemica l Informatio nServices , Stanfor d Researc h Institute , Menl o Park , C A (Jul y 1977)] . g Georgia-Pacifi c Corporatio ni n 197 9 state d thei r Columbus , Coo s Bay , and Russellvill e capacitie s t o b e 32 , 34 , an d 9 0 Gg/y r (pe r lette r date d Ma y 30 , 1979 , fro

m V . J . Tretter , Georgia-Pacific , t o R . T . Walsh , EPA) . I n 197 6 Roh m an d Haa s close d a n11-Gg/y r plan t a t Phila delphia , PA , an d Unio nCarbid e close d a 54-Gg/y r plan t a t Boun d Brook , NJ .P.6 1



### III- l 

# mm

III . PROCES S DESCRIPTIO N
INTRODUCTIO

N I n th e Unite d State s tw

o majo r processe s are use d in th e manufactur e o f formalde hyd e fro m methanol : th

e metallic-silver-catalys t combinatio n dehydrogenation oxidatio

n proces s (silve

r process) , whichi s use d a t 3 5 location s t

o produc e 75 % o f th e formaldehyd

e manufactured , an

d th e metal-oxide-catalys t oxidatio nproces s (meta l oxid

e process) , whichi s use d at 2 0 location s to produc e 25 % o f th e formal dehyd e manufactured . Th e projected annua l productio n growthfo

r eac hproces s i s 4 to 5%. 1, 2


### Tw o gas-phas e reaction s ar e employe

d t o for m formaldehyd

e fro m methanol : Reactio n 1 — Dehydrogenatio

n
CH 3 

### 0 H (methanol ) HCH O (formaldehyde ) H 

### 2 (hydrogen ) Reactio n 2 — Oxidatio

n
C H O H + (methanol ) (oxygen ) -> - HCH

O + (formaldehyde ) H 2 

### 0

(water )
Th e silver proces s involve s th e dehydrogenatio

n o f methano l (reactio n 1 ) followe

d b y oxidatio

n o f a portio

n o f th e hydrogen evolve

d to for

m water , o

r a combinatio

n o f dehydrogenatio

n an d oxidatio

n o f methano l (reaction s 1 an d 2) . Th

e meta l oxid

e 3 proces s involve s oxidatio n o f methano l b

y reactio

n 2 . Th e majo r differenc e between th e tw o processe s i s th

e amount o f ai r mixed wit h th e methano l befor e conversion . Sinc e ai r an d methano l for

m explosiv

e mixture s a t concentration s o f approximatel y 6 t o 3 7 vo l % o f methano l i n air , th

e air / methano l inpu

t mus t b

e controlled . Th

e metallic-silver-catalys t dehydrogenation oxidatio

n processe s maintai na n exces s o f methanol , an d methano l concentration s ar e abov e th e explosiv

e range , wherea s th e metal-oxide-catalys t oxidatio n proc esse s us e a

n exces s o f ai r so tha t th e methano l concentration s are belo w th e lower limit s o f th

e explosiv

e range . Off-ga s fro m th e metallic-silver-catalys t proces s contain s 1 8 t o 20 % hydrogen an d les s tha

n 1 % oxygen . Off-ga s fro m th e metal-oxide -P.6 2 *^a*amm*^nwmw


### III- 2

> catalys t proces s contain s unreacte d oxyge n an d n o appreciabl e concentratio no f hydrogen . Withth e metallic-silver-catalys t proces s th e exces s methano l mus t be separate d t o mee t custome r specifications . Wit hth e metal-oxide-catalys t proces s th e larg e exces s o f ai r require s a larger compressor an d th e proces s equipmen t mus t b e large r t o handl e th

e adde d ai r volume . METALLIC-SILVER-CATALYS T PROCES S
Proces s Descriptio

n Th e proces s flo

w diagra m show n i n Fig . III- l represent s a typica l continuou s metallia silver-catalys t process . Th e incomin

g ai r (Strea

m 1 ) i s washe

d wit hcausti c t

o remov e trace s o f sulfu

r dioxide , hydrogen sulfide , an d othe r impuritie s that ac t a s catalys t poisons . ' Th e ai r i s the

n compresse

d t o 14 3 kPa an

d passed throug

ha vaporize r column , wher e i i t i s heate

d an d saturate

d wit hmethano l vapo r (Strea m 2) . Th

e heate d ai r an

d methano l vapo r mus t compris e mor e tha n 3 7 vo l % methano l in orde r to b e abov e th e hig hexplosiv

e limi t o f th

e methanol . Th e mixtur e (Strea

m 3 ) the n enter s a batter

y o f converters . Approximatel y 80 % o f th e methano l fee

d i s reacte

d fo r a per-pas s conversio n rati o o f 0.80 . Th e converte

r temperature i s maintained a t approximatel y 635° C (ref . 5 ) b

y hea t generate

d b y th e oxidatio

n o f a portio

n o f th e hydrogen evolve

d and/or b

y methano l oxidation . Th e ho t effluent gase s (Strea m 4 ) are quickl y

coole d to preven t decompositio no f th e formaldehyd

e formed . Coolin

g i s accomplishe

d b y hea t interchange wit hth e fee d mixtur e in th

e vaporize r an

d b y the n introducin

g th e ga s int o th

e primar

y absorber . Th e primary-absorbe r liqui d i s a n aqueou s solutio

n o f formaldehyd

e an d methanol . A portio n o f thi s liqui d i s withdraw n fro m th e botto m o f th e absorbe r colum

nan d recirculate

d to th e top . Th

e remainde r (Strea

m 5 ) i s pumpe

d to th e produc t frac tionatio

n column . Th

e uncondensed vapor s an d noncondensabl e gase s (Strea m 6 ) are withdraw

n fro m th e to p o f th e primary-absorbe r colum n an d fe d t o a secondar

y absorb eA < P O

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### Fig . III-l . Flo w Diagramfo r Uncontrolle d Mode l Plan t Producin g Formaldehyd e fro m Methano l wit h th e Metallic-Silver-Catalys t Proces sP.6 4

III- 4

Th e majo r portio n o f the uncondense d vapor s i s recovere d i nthe secondary-absorbe * colum n throug hcontac t wit hdemineralize d water , and the off-ga s i s vente d (Ven t Th e weak formaldehyde/methano l solutio n(Strea m 7 ) withdraw

nfro m th e bottom

o f th e secondary-absorbe r colum ni s pumpe d t o the primary-absorbe r colum n and use d a s makeu p solution .
Th e methanol-containin g formaldehyd e solutio n(Strea m 5 ) i s pumpe d t o a fractiona tio n column , where methano l i s recovered . Thi s vacuu m distillatio n ste p yield s a n overhea d produc t o f approximatel y 99 % methano l fo r recycl e t o the reacto r and a botto m produc t o f formaldehyd e solutio ncontainin g les s tha n1 % methanol . Th e * methano l vapo r fro m th e to p o f the colum ni s condense d an d recycle d t o the vapori z (Strea m 9) . Uncondense d vapor s ar e vente d (Ven t B) . Th e formaldehyd e solutio n fro m th e bottom

o f th e fractionatio ncolum ni s pumpe d t o produc t storag e tanks . Whenrequire d by

custome r specification s th e solutio ni s treate d fo r remova l o f trac e amount s o f formi c aci d b y bein g passe d throug ha nionexchang e syste m befor e bein g stored . A s a fina l step , wate r i s adde d t o provid e a suitabl e concentratio n fo r storag e an d shipping . Reporte d yield s fo r the metallic-silver-catalys t proce s rang e fro

m 8 3 t o 92%. 1 '
Al l produc t storag e tank s ar e heate d t o preven t polyme r formatio n an d precipita tio n i nstorage . A serie s o f tank s ar e use d t o blen d an d adjus t the solutio n to th e desire d formaldehyd e an d methano l concentration s befor e i t i s shippe d t o the customer . .
Proces s Variation s Vacuu m distillatio n i s describe d fo r the model-plan t proces s ste p use d fo r recover o f the exces s methano l i nth e produc t stream . However , the uncondense d gase s an d vapor s discharge d fro m th e vacuu

m produce r mus t be vente d o r otherwis e deal t with . Many plant s us e pressure distillatio nequipmen t operate d a t increase d temperatur e instea d o f vacuu

m fractionation , whic hdispense s wit hthe nee d fo r th e ven t assoc : ate d wit hth e fractionato r vacuu m produce r (Ven t B , Fig . III-l ) and therefor e eliminate s th e emissio nsource . The quantit y o f dissolve d gase s i n th e fee d t o the distillatio n colum ni s ver y

small .
Proces s developmen t effort s hav e bee ndirecte d towar d reducin g th e exces s methan o i n orde r t o eliminat e the fractionatio nstep . Th e additio no f wate r t o th e meth aP.6 5



### III- 5

t o for m a fee d mixtur e containin g 3 0 t o 5 0 vo l % wate r ca n produc e a produc t con tainin g 7 t o 8 w t % methanol , som e markets . Thi s concentratio n o f methano l i s suitabl e fo r

Man y approache s hav

e been take

n b y th e variou s plant s t

o improv

e efficienc

y fo r hea t utilization . In som e plant s hea t fro

m th e reactor i s used to hea t th e methano l distillatio n reboiler o

r t o generat e stea

m t o driv e th e fractionation colum n vacuu m pump . C . METAL-OXIDE-CATALYS T PROCES S
1 . Proces s Descriptio n Th e proces s flo

w diagra m show n in Fig . III- 2 represent s a typica l continuou s metal oxide-catalys t process . Th e catalys t syste

m mos t ofte

n used i s ferri c molybdate . Incomin g ai r (Strea

m 1 ) ma y be washed wit hcausti c solutio n i n a packed tower t o remov e dus t an

d trac e impurities . Th e ai r i s the

n compressed , alon

g wit hth

e recycl e ga s (Strea

m 5 ) t o 14 3 kPa . Recycl e o f a portio n o f th e oxygen-lea

nvent gase s lower s th

e oxyge n content o f th

e ai r fee

d strea m t o belo w 10.9% . Thi s re duce s th

e explosio

n hazar d o f th e fee d mixtur e an

d increase s th

e equipmen t outpu t b y reducin

g th e amount o f exces s ai r require d t o kee p th e methano l concentratio n belo w th e lo w explosiv

e limit .
A portio n o f th e ai r i s passed throug hth e vaporize r column , wher e i t i s saturated wit hmethano l (Strea m 2) . Th

e methanol-saturated ai r i s the n mixed withth

e remain in g ai r an

d preheated b

y hea t exchange wit hth e produc t ga s leavin g th e converter . Th e fee d ga s mixtur e (Strea m 3 ) the n enter s th

e converter . Conversio nratio s o f 97 % are obtained . Th e converter , heated b y th e exothermi c oxidatio n reaction , i s maintained a

t 345° C (ref . 5 ) b

y boilin g hea t transfer flui d i n th e reactor shell . Stea m i s generate

d b y condensatio

n o f th e heat-transfe r flui d vapors . 

# ± Th

e produc t ga s (Strea m 4 ) i s cooled b

y hea t exchange wit hth e fee d ga s mixtur e an d the n quenche

d in th e absorbe r column . Th e formaldehyd

e an d methano l are re moved fro

m th e ga s strea

m b y absorptio

n in th e aqueou s solution . Th e unabsorbed gase s an

d vapor s exi t at th e to p o f th e absorbe r column . A portion (6 0 t o 80% ) o f thi s ga s i s recycle d (Strea

m 5 ) an d th e remainin

g ga s i s vented . Th e produc t***am*a*m



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### 1 . III- 7

solutiondraw

n fro m the bottom

o f the absorbe r colum ncontain s approximatel y 0.8 % methano l an d 0.005 % formi c acid . Th e solutio ni s usuall y treate d i na nio n exchang e syste m t o reduc e the acidit y an d i s the nstored . A s a fina l ste p wate r i s adde d t o provid e a suitabl e concentratio nfo r storag e and shipping . Proces s yield s o f 9 1 t o 93 % ar e reporte d fo r the metal-oxide-catalys t process . '
Th e formaldehyd e yiel d fro m th e metal-oxide-catalys t proces s i s highe r tha n tha t fro m the metallic-silver-catalys t proces s an d the metal-oxide-catalys t proces s i s simpler , because methano l distillatio ni s no t required . Th e equipmen t cost s fo r th e metal-oxide-catalys t proces s ar e greate r becaus e o f the larg e volum e ga s streams, - also , becaus e o f a lowe r concentratio no f formaldehyd e i nthe produc t ga s stream , the absorbe r colum ndiamete r i s large r an d the operatin g temperatur e i s lowe r tha n thos e use d wit hth e metallic-silver-catalys t process .
Proces s Variation s Th e industr y

make s us e o f variou s catalys t composition s an d method s an d exten t o f hea t recovery . Otherwise , th e processe s use d ar e basicall y similar . Man y

olde r plant s d o no t recycl e a portio no f the absorber-colum nven t gas . Fo r thes e plant s th e ven t ga s volum e and th e rati o o f volatil e organi c compound s emitte d pe r uni t o f produc t produce d ar e increased .
Th e oxid e catalys t i s no t susceptibl e t o poisonin g by trace s o f sulfide s i n the ai r feed ; thu s many plant s filte r the incomin g ai r rathe r tha nutilizin g causti c scrubbers .
OTHE R PROCESSE S Formaldehyd e by

Partia l Oxidatio no f Methan e Considerabl e researc hha s bee ndevote d t o productio no f formaldehyde directl y fro m methane . Th e proces s i s more comple xand require s a highe r capita l invest men t tha n d o processe s utilizin g methanol . Commercia l attempt s t o produc e formal dehyd e fro

m natura l ga s o r methan e ha s ha d limite d succes s an d th e proces s cur rentl y i s no t use d i n the Unite d States .

Z9' dIV- 1

IV . EMISSION S
Emission s i n thi s repor t ar e usuall y identifie d i nterm s o f volatile organi c com pound s (VOC) . VO C ar e currentl y considere d b

y th e EP A t o be thos e o f a larg e grou p o f organi c chemicals , mos t o f which , whe nemitte d t o the atmosphere , parti cipat e i n photochemica l reaction s producin g ozone . A relativel y

smal l numbe r o f organi c chemical s hav e lo w o r negligibl e photochemica l reactivity . However , many o f thes e organi c chemical s ar e o f concer nand ma y b e subjec t t o regulatio n b y EP A unde r Sectio n 11 1 o r 11 2 o f the Clea nAi r Ac t sinc e ther e ar e associate d healt h o r welfar e impact s othe r tha nthos e relate d t o ozon e formation .
Th e proces s emission s estimate d fo r the formaldehyd e mode l plant s ar e base d o n th e emission s reporte d i n response s t o EPA' s request s fo r informatio nfro m selecte d companies , o n EP A

emissio n testin g data , an d o ndat a obtaine d durin g visit s t o Ceianes e and Borde n formaldehyd e productio nplant s (se e Appendi xE) . Als o use d i nsizin g an d desig n o f the mode l plant s were dat a fro m the EP A

studies , SR I reports, : formaldehyd e dat a compile d b y J . F . Walker , an d a nunderstandin g o f th e proces s chemistr y and yields . 

### A . FORMALDEHYD E FRO M METHANO L PROCES S USING A METALLI C SILVE RCATALYS T

l
- Mode l Plan t Th e mode l plant * fo r thi s stud y ha s a capacit y

o f 4 5 Gg/yr , base d o n876 0 h r o f operatio npe r year.* * Althoug hno t a nactua l operatin g plant , i t i s typica l o f man y plant s buil t recently . Th e plan t utilize s the mode l metallic-silver-catalys t proces s (Fig . III-l ) an d bes t fit s today' s formaldehyd e manufacturin g and engi neerin g technolog y fo r tha t process . Typica l raw-material , intermediate, an d product-storag e tan k capacitie s wer e esti mate d fo r the 45-Gg/y r mode l plant . Storag e tank requirement s ar e give n i n Sect . IV.A.2.e . Estimate s o f potentia l fugitiv e sources , base d o ndat a fro m existin g *Se e p . 1- 2 fo r a discussio n o f mode l plants . *Proces s downtime i s normall y expecte d t o rang e fro m 5 t o 15% . I f the hourl y rat e remain s constant , th e annua l productio nan d annua l VO C emission s wil l be correspondingl y

reduced . Contro l device s wil l usuall y operat e o nth e same cycl e a s th e process . Fro

m th e standpoin t o f cost-effectivenes s calculations , th e erro r introduce d b y assumin g continuou s operatio ni s negligible .

### IV- 2

plants , ar

e given in Sect . IV.A.2.d . " " Characteristic s o f th e mode l plan t that are importan

t i n air-dispersio

n modelin

g ar e show n in Appendi xB . Source s an

d Emission s Uncontrolle

d emissio

n rate s an

d source s fo

r th e metallic-silver-catalys t proces s ar e summarize

d in Tabl e IV- 1 an d ar e describe

d below . Th

e proces s emissio

nrate s ar e base d o n emissio

n dat a fro

m existin

g plants . Potentia l storage , handling , fugitive , an

d secondar

y emission s wer e calculate d fro m characteristic s o f th e plan t an

d fro m dat a o n existin

g plant s (se

e Tabl e IV-2) . Absorbe r Vent —

Th e absorber vent (Ven t A , Fig . III-l ) i s th e principa l sourc e o f emission s fro

m th e formaldehyd

e productio

n plant . Th

e volatil e organi c compound s (VOC ) i

n th e vent ga s includ

e unreacte

d methanol , formaldehyde , methy l formate , an

d methyla l (se

e Tabl e IV-3) . Als o include d in th e vent ga s ar

e hydrogen , methane , carbo

n monoxide , carbo

n dioxide , nitrogen , wate r vapor , an d a smal l amoun

t o f unreacte

d oxygen . Th

e compositio

n o f th e absorber vent varie s somewha t wit h th e catalyst' s ag

e an d < i s give n i n Tabl e IV-1 . 4 th e catalyst' s ag

e an d activity . Th

e average emissio

n durin g norma l operatio

n

Produc t Fractionator Vent — A produc t fractionator operate d unde r vacuu

m i s used t o separat e an

d recover unreacte

d methano l fro

m th e produc t stream . A stea m ejecto r o r vacuu m pum p i s employe

d t o produc e th

e vacuu m required . Emission s fro m thi s sourc e (Ven

t B ) includ

e methano l vapor , formaldehyde , wate r vapor , an d a smal l amount o f inert gase s (se e Tabl e IV-3) . Intermittent Ai r Emission s — Th e formaldehyd

e plant i s normall y operate

d a t desig n condition s t

o achiev

e highes t yields . I t i s shu t dow n when produc t inventorie s ar e filled . Sinc e th e metallic-silver-catalys t proces s operate s abov e th e uppe r explosiv

e limi t o f methanol , th e plant startu

p procedur e mus t b

e handle

d carefully . Unstabl e condition s ar e ofte n encountered an

d explosion s ca

n occu r in th e methano l vaporize r an

d th e reactor . Variou s startu p procedure s ar

e used in th

e industry . Usuall y durin g startu

p th e output fro

m th e reactor i s vented unti l stabl e operatio n i s achieve

d an d a n acceptabl e yiel d rati o i s obtained . Th e flo w i s the n switche

d ' 2 int o th e absorber . Th

e tota l startu

p tim e i s 1 t

o 2 hr . Th

e reactor fee

d rat e varie s a s th

e startu

p proceeds . Initiall y th e reactor produce s mainl y carbo nP.7 0



### IV- 3

Tabl e IV-1 . Tota l VO C fro mUncontrolle d Emission s Produce d b y Formaldehyd e Metallic-Silver-Catalys t Proces s i n a Mode l Plan t

Emissio n Sourc e Strea m Designatio n (Fig.III-l ) Emission s

Absorbe r Product fractionato r b Intermitten t Hethano l storag e Formaldehyd e storag e Handlin g Fugitiv e Secondar y Tota l A B C D D F H K 

### Ratio a 

### (g/kg j 4.7 3 1.5 6 0.1 1 0.0 8 0.0 3 0.0 1 1.0 8 0.0 1 Rat e

(ka/hr ) 24. 5 8. 2 

### 0.2 8 0.4 3 0 . 2 0 . 1 

### 5. 7 . 0.0 3 7.6 3 39.4 4 9 o f tota l VO C pe r k g o f 37 % formaldehyd e solutio n produced . b Averag e rat e fo r

entir e year , base do n 8 startup s pe r yea r an dflo w o f

one-hal f

th e norma l rat e durin g startup . Tabl e IV-2
. Mode l Plan t Storag e 

# 1 1 _^onten t

Ethano l (feed ) formaldehyd e Methano l (recycle )

Me 

### thano l (feed ) p 

### °rmaldehyd e Tan k Siz e No . o f

Tank s Turnover s (m^) Require dPe r Yea r Metallic-Silver-Catalys t Proces s 19 0 2 6 8 19 0 4 4 5 4
. 1 *

Metal-Oxide-Catalys t Proces s 19 0 2 6 5 19 0 4 4 5 Bul k Liqui d Temperatur e ~(°C)

2 5 5 4 3 8

2 5 5 4

s 

### urg e tank
. 

# IP.7 1



### IV- 4
Tabl e IV-3 . Emissio n Compositio n fo r Mode l Metallic-Silver-Catalys t Process 6



### Componen t VOC 

### Formaldehyd e Methano l Methy l format e , Methyla l , Combustibl e gase s ' Hydroge n Methan e Carbo n monoxid e Othe r gase s Oxyge n Nitroge n Carbo n dioxid e Wate r vapo r Tota l Absorbe r Compositio n (w t % ) 0.7 5 (0.06 ) (0.14 ) (0.36 ) (0.19 ) 2.3 8 (1.69 ) (0.28 ) (0.41 ) 93.9 6 (0.42 ) (86.64 ) (6.90 ) 2.9 1 100.0 0 Ven t

Rati o (g/kg ) 4.7 3 (0.36 ) (0.89 ) (2.27 ) (1.20 ) 14.9 7 (10.59 ) (1.77 ) (2.61 ) 590.2 3 (2.63 ) (544.23 ) (43.37 ) 18.2 5 628.1 7 Emission s Fractionato r

Compositio n . (w t % ) 83.1 6 (17.49 ) (65.67 )

0.9 4

15.9 0 100.0 0 Ven t o 4.- b 

### Rati o (g/kg) . 1.5 8 (0.33 ) (1.24 )

0.0 2

0.301 3 1.9 0 Emissio n rate s ar e base d o n emissio n dat a fro mexisting plants ; se e Appendi x E . g o f emissio n pe r kg o f 3 7 w t % formaldehyd e solutio n produced .P.7 2



### IV- 5

dioxide an

d wate r vapor . A s the temperature rises , the formaldehyd e yiel d in

creases , thereb

yenlargin g the amoun t o f VO C i n the ga s vented . Th e averag e annua l emission calculate d fro mthi s sourc e (se e Tabl e IV-1 ) i s base d o n a n averag e o f eight startup s pe r yea r an d a flow o f one-hal f the norma l rat e durin g startup . d . Fugitiv

e Emission s - - Proces s pumps , valves , and circulatin g proces s coolin g wate r are potentia l source s o f fugitiv e emissions . Th e mode l plan t i s estimate d t o 1-- 3 hav e 1 3 pumps , 21 4 proces s valves , an d 6 relie f valve s handlin g VOC . A n esti

mate d 6. 5 liter s o f cooling wate r pe r k g o f produc t produce d i s circulate d through th e cooling tower . Fugitiv e emissio n factor s fro mAppendi x C wer e applie d t o determin e the fugitiv e emission s show n i n Tabl e IV-1 .
e . Storag e an

d Handlin g Emission s —Emission s resul t fro mthe storag e an

d handlin g o f methano l an

d formaldehyde . Source s fo r the mode l plan t ar e show n i n Fig . III- l (Sourc e D) . Storag e tan k condition s fo r th e mode l plan t ar e give n i n Tabl e IV-2 . Th e emission s i n Tabl e IV- 1 ar e base d o n fixed-roo f tanks , hal f full , an d a diurna l temperatur e variatio n o f 11.1° C an d wer e calculate d base d o n the emissio n equation s fro mAP-42 . However , calculate d breathin g losse s wer e divide d b y4 t o accoun t fo r recen t evidenc e indicating tha t the AP-4 2 breathin g los s equatio n overpredict s

. . 6 emissions . Sinc e uninhibite d formaldehyd e polymerize s a t a low temperature , concentrate d solution s (ove r 30 % HCHO ) mus t b e kep t warm . Therefor e the model-plan t formal
dehyd e storag e tank s ar e maintaine d a t abov e 54°C . Sinc e thes e tank s ar e tempera tur e controlled , breathin g losse s ar e negligibl e an d emission s give n ar e base d o n working losse s only . Emission s fro

mthe loading o f formaldehyd e solutio n int o truck s an d tan k car s wer e calculate d wit h the equation s fro mAP-42 , wit h submerged-fill-pip e loading assume d t o b e used . Thes e emission s ar e als o include d i n Tabl e IV-1 . Secondar

yEmission s - - SecondaryVO C emission s ca n resul t fro mthe handlin g and disposa l o f process-wast e liqui d streams . Th e potentia l source s (Sourc e K ) tha t exis t fo r th e mode l plan t are io n exchang e systemregeneratio n an d blowdow

n wate r fro mth e coolin g and air-was h towers . Th e calculate d tota l secondaryVO C emis

sio n fro

mthes e source s i s give n i n Tabl e IV-1 . Calculation s ar e based o

nwaste -IV- 6

wate r dat a reporte d b y industr y

an d the assumption s tha t the io nexchang e syste m i s operate d fo r 10 % o f th e productio ne wastewate r evaporate s befor e treatment . i s operate d fo r 10 % o f th e productio nand tha t 5 % o f the VO C containe d i n th e '

B . FORMALDEHYD E FRO M METHANO L PROCES S USING A META L OXIDE CATALYS T
1 . Mode l Plan t Th e mode l plan t fo r thi s study i s base d o nthe metal-oxide-catalys t proces s utilizin g ven t ga s recyclin g (Fig . III-2) . Thi s mode l proces s bes t fit s today' s formaldehyd e manufacturin g an d engineerin g technolog y fo r utilizin g a meta l oxid e catalyst . Th e mode l plan t ha s a capacit y o f 4 5 Gg/y r base d o n876 0 h r o f operation pe r year . Typica l raw-materia l an d product-storag e tank capacitie s were estimate d fo r th e 45-Gg/y r mode l plant . Storag e tank requirement s ar e give ni nSect . IV.B.2.e . Estimate s o f potentia l fugitiv e sources , base d o ndat a fro m existin g plants , ar e give n i n Sect . IV.B.2.d . Characteristic s o f t * i n air-dispersio n modelin g ar e give ni nAppendi xB . give n i n Sect . IV.B.2.d . Characteristic s o f the mode l plan t tha t ar e importan t

Source s and Emission s Uncontrolle d emissio n rate s an d source s fo r the metal-oxide-catalys t proces s ar e summarize d i n Tabl e IV- 4 an d ar e discusse d below . Proces s emissio nrate s ar e base d o n emissio n dat a fro m existin g plants . Potentia l storage , handling , fugitive , an d secondar y

emission s wer e calculate d fro m model-plan t characteristic s an d dat a fro m existin g plants . Sinc e the proces s operate s belo w th e explosive limi t wit ha nexces s o f air , unstabl e condition s durin g startu p ar e easil y prevented . Ventin g o f the reacto r durin g startu p i s no t required . Absorbe r Ven t - - Th e produc t absorbe r ven t (Ven t A , Fig . III-2 ) i s th e mai n sourc e o f emission s fro

m the formaldehyd e productio nplant . Th e VO C component s i n th e ven t ga s includ e methanol , formaldehyde , an d dimethy l ethe r (Tabl e IV-5) . Als o include d i n th e ven t ga s ar e carbo nmonoxide , carbo ndioxide , nitrogen , oxygen , an d wate r vapor .P.7 4



### > n IV- 7

Tabl e IV-4 . Tota l VO C Uncontrolle d Emission s fo r Formaldehyd e Produce d b

yMetal-Oxide-Catalys t Proces s i n a Mode l Plan t

Strea m Designatio n Source (Fig.III-l ) Absorbe r Methano l storag e Formaldehyd e storag e Handling Fugitiv e Secondar y Tota l A D D F H K Rati o (g/kg) a 

### 3.1 5 0.0 8 0.0 3

. 0.0 1 0.7 4 0.0 5 Emission s Rat e

(kg/hr ) 16. 3 0.4 4 0. 2 0. 1 3. 7 0. 2 4.0 6 20. 7 g o f tota l VO C pe r k g o f 37 % formaldehyd e solutio n produced .P.7 5



### IV- 8

Tabl e IV-5 . Absorbe r Ven t Ga s Compositio n fo r Mode l Metal-Oxide-Catalys t Process 3


### Emission s Componen t Compositio n (w t % ) 0.2 7 (0.04 ) (0.16 ) (0.07 ) 95.4 5 (7.91 ) (86.09 ) (0.19 ) (1.26 ) 4.2 8 100.0 0 Rati o (q/kq ) 3.1 5 (0.44 ) (1.93 ) (0.79 ) 1124.3 9 (93.20 ) (1014.02 ) (2.28 ) (14.89 ) 50.37 ) 1177.9 1 VO C Formaldehyd e Methano l Dimethy l ethe r Othe r gase s Oxyge n Nitroge n Carbo n dioxid e Carbo n monoxid e Wate r vapo r
Emissio n rate s ar e base d o n emissio n dat a fromexisting plants ; se e Appendi x E . 3 

### g o f emissio n pe r kg o f 3 7 w t % formaldehyd e solutio n produced .



## •a nP.7 6

IV- 9

The emissio n compositio n an d flo w rate s ar e especiall y affecte d b y

th e percen t o f absorbe r ga s recycled . B y recyclin g a portio no f the oxygen-lea n ven t gas , th e oxyge nconcentratio n i n th e reacto r fee d mixtur e ca nbe reduced , makin g i t possibl e for the concentratio n o f methano l t o b e increase d withou t anexplosive mixture bein g formed . Thi s reduce s the volume o f reactio n gase s and thu s reduce s equip men t siz e an d horsepowe r require d t o driv e the compressor . Recyclin g reduce s the 9 emissio n rat e an d enhance s the reacto r equilibriu m t o produce a highe r yield . Th e effec t o f recyclin g o n absorbe r ven t emission s ca nb e see nb y the compariso n o f absorbe r ven t ga s compositio nfo r recyclin g an d nonrecyclin g operation s give n i nTabl e IV-6 .
Othe r variable s tha t affec t the absorbe r ven t emission s ar e catalys t formulation , catalys t age , absorbe r temperature , an d strengt ho f formaldehyd e produced . Th e catalys t formulatio n ca n affec t th e overal l proces s yiel d an d thu s the amoun t and type o f by-product s o r emission s produced . Also , produc t yield s tend t o decreas e a s th e catalys t ages . Lowerin g the absorbe r temperatur e increase s it s efficienc y an d thu s lower s th e VO C emission s fro m th e absorber . A s the strengt ho f the for maldehyd e produce d increases , the partia l pressure du e t o the formaldehyd e increases , thu s increasin g th e relativ e amoun t o f formaldehyd e i nthe ven t emission .
Th e model-plan t averag e absorbe r ven t emissio ndurin g norma l operatio n i s give n i nTabl e IV-4 . A recycl e rat e o f 6 3 vo l % fo r the produc t absorbe r ven t ga s wa s calculate d base d o n emission s data . Fugitiv e Emission s — Proces s pump s an d valve s ar e potentia l source s o f fugitiv e emissions . Th e mode l plan t i s estimate d t o hav e 8 pumps , 17 6 proces s valves , an d 4 relie f valve s handlin g VOC . A nestimate d 6. 5 liter s o f coolin g wate r pe r k g o f produc t produce d i s circulate d throug hthe coolin g tower . Fugitiv e emissio n factor s fro m Appendi xC were applie d t o determin e the fugitiv e emission s show n i n Tabl e IV-4 . Storag e an d Handlin g Emission s — Emission s resul t fro m th e storag e and handlin g o f methano l an d formaldehyde . Source s fo r the mode l plan t ar e show ni n Fig . III- 2 (Sourc e D) . Storage tan k condition s fo r th e mode l plan t ar e give ni nTable IV-2 . Th e emission s i n Tabl e IV- 4 ar e base d o nfixed-roo f tanks , hal f full , and a diurna l temperatur e variatio n o f 11.1° C an d wer e calculate d base d o nth e emissio nequation s •P.7 7



### IV-1 0
Tabl e IV-6 . Absorbe r Ven t Emissio n Ratio s fo r Recycle d Ven t Ga s v s Nonrecycle d Ven t Ga s fo r Mode l Metal-Oxide-Catalys t Proces s J^rrossiq

n Rati o (gAg ) Recycle d Nonrecycle d Componen t Ven t Ga s Ven t Ga s Tota l VO C 3. 2 12. 7 Other C 

### 1174. 8 5440. 0 Tota l 1178. 0 5452. 7

a 

### g o f tota l VO C pe r k g o f 37 % formaldehyd e solutio n produced . Include s formaldehyde , methanol , an d dimethy l ether . c • • Include s nitrogen , oxygen , carbo n dioxide , carbo n monoxide , an d water .

• ^ ,P.7 8



### IV-1 1

fro mAP-42 . However , the breathin g losse s wer e divide d b y4 t o accoun t fo r recen t evidenc e indicating tha t th e AP-4 2 breathing-los s equatio n overpredict s emissions .



### d . Sinc e uninhibite d formaldehyd e polymerize s a t low temperature , concentrate d solu
7 tion s (ove r 30 % HCHO ) mus t b e kep t warm . Consequentl ythe model-plan t formalde
hyde storag e tank s ar e maintaine d abov e 54°C . Breathin g losse s ar e negligibl e becaus e the tan

k temperatur e i s controlled . Emission s therefor e ar e base d o n onlyworkin g losses . Emission s fro

mthe loading o f formaldehyd e solutio n int o truck s an d tan k car s wer e calculate d wit h the equation s fro mAP-42 . Thes e emission s ar e include d i n Tabl e IV-4 . Secondar

yEmission s - - SecondaryVO C emission s ca n resul t fro mthe handlin g an

d disposa l o f process-wast e liqui d streams . Th e potentia l source s (Sourc e K ) tha t exis t fo r the model-plan t ar e io n exchang e syste mregeneration , blowdow n wate r fro mthe cooling an

d air-was h towers , an d emission s fro

mthe heat-transfe r flui d syste mvent . Th e tota l secondar yVO C emissio n fro

mthes e source s i s give n i n Tabl e IV-4 . Emission s wer e calculate d base d o n wastewate r dat a reporte d b yindustry an d th e assumption s tha t the io n exchang e syste mi s operate d fo r 100 % o f the produc
tio n an d tha t 5 % o f the VO C containe d i n th e wastewate r evaporate s befor e treatment .

# Introductio n t o

Industria l Chemistr y
HOWAR D L . WHIT E CIBA-GEIG Y Corporatio n (Ret. )

A Wiley-lnterscienc e Publicatio n 

## JOH N WILE Y & SON S Ne wYork •Chicheste r •Brisban e •Toronto •Singapor eP.8 0


# jr^&m

who :
an dv
( w a n

Copyrigh t© 198 6 b

y Joh n Wile y & Sons , Inc . Al l rights reserved . Publishe d simultaneousl y i n Canada. Reproduction o rtranslation o f an y par to f thi s wor k beyond tha

tpermitted by Sectio n 10 7 o r108 o f

the 1976 Unite d State s Copyrigh tAc twithoutthe permissio n o f th e copyrigh towne ri s unlawful . Request s for permissio n o rfurthe

rinformatio n shoul d b e addressed t o th e Permission s Department, Joh n Wile y & Sons , Inc . Library of

Congress Cataloging in Publication Data: White , Howard L. , 1922 - Introduction t

o industria

l chemistry .
" A Wiley-lnterscienc e publication. " Includes bibliographie s an d index . 1 . Chemistry , Technical . I . Title . TP145.W4 6 198 6 ISBN 0-471-82657- X 660. 2 86-564 3 Printe d i n th e Unite d State s o f

America 10 9 8 7' 6 5 4 3 2 110 6 ORGANI C CHEMICA L PROCESSE S Anothe rsourc e o f malci c ;inhydrid c i s th e mothe rliquor s o f th e phthali c anhydrid e process usin g th e naphthalen e process . 4. 8 INDUSTRIA L CHEMICAL S FRO M METHAN E W c have no w discusse d si xo f th e seve n chemica l substance s derive d fro m petroleu m Fro m thes e petrochemical s ar e derive d 90 % o f al l commerciall y prepare d organi c substances
. Th e sevent h i s methane , whic h w c hav e encoun tere d fou rtime s befor e i n thi s hook : First , ther e wa s th e synthesi s o f ammoni a fro m nitroge n an d hydrogen
. Ih e latte rderive d fro m methan e an d stea m b yth e reactio n formin g synthesi s gas . a carrio n monoxide-hydroge n mixtur e (se e Sec tio n 2.3.1.A)
. Second , w e discusse d th e significan t quantit yo f methan e avail abl e fro m anaerobi c digestio n o f sewag e sludg e (se e Sectio n 3.2.4.B)
. Third , w c discusse d th e hydroformylatio n reaction , additio n o f methane-derive d syn thesi s ga s t o olefin s t o yiel d aldehyd e mixture s (se c Sectio n 4.3.3)
. Fourth , th e preparatio n o f mclhano l fro m synga s wa s discusse d i n detai l i n Sectio n 4.2.5
. W c no w discus s variou s large-scal e product s tha t us e methano l i n thei rman ufacture
. Th e approac h i s tha t o f Fran k (I982)
. wh o discusse d thes e product s unde rtw o headings : (I ) traditiona l use s o f mclhanol
. an d (2 ) ne w an d evolvin g use s o f methanol
. W c firs t briefl yrevie w th e traditiona l uses : 4.8. 1 Traditiona l Uses o f Methano l A. Formaldehyde Th e manufactur e o f fonnaldchyd c i s carrie d ou i b yremova l o f hydroge n fro m methano l b ya catalyti c process . Thi s proces s wa s referre d l o i n th e discussio n o f ethylen e glyco l i n Sectio n 4.2.9.A
. Th e mos t up-to-dat e process involve s th e us e o f silve rneedle s o rgau/c s at 600T
. Th e methano l i s expose d fo rabou t , t ' 0.0 1 second , an d ver ylittl e mclhano l i s left
. Ai ri s adde d l o Ih e mixtur e to^ y combin e wit h th e hydrogen
. Thi s liberate s heal , whic h i s neede d fo rth e cn dolhermicVlchydrogciialio n slcp j Thi s silve rcatalysi s reactio n resemble s th e ethylen e oxid e synthesi s i n tha t th e meta l significantl yreact s onl ywhcn.i l i s covere d wit h a laye ro f oxygen . Th e mechanis m i s show n i n thes e tw o equations : A q CHjOH,, , . 0, ad M • CH,0 (ad5 1 + OH,,* , fiOO-C CH 3 O IMS | • CHpOu, , t H (adS | Fo ra furthe rrevie w o f thi s topic , se c Rylandc r(1983
. pp . 19-20)
. 

# (jijU ^
107 4. 8 INDUSTRIA L CHEMICAL S FRO M METHAN E B. Dimethyl

Terephthalate

(DMT) Polyeste rlibe ri s mad e fro m th e ra w material s dimethy l terephthalat e an d ethylen e glyco l

nCH 3 OOC-C 6 H 4 -COOCH 3 + r»HOCH,CH 2 O H I -OOC-C 6 H 4 -COOCH ? C H 2 - + 2nCH 3 O H Th e proces s use s p-xylen e as a ra w materia l an d i s a catalyze d ai roxidation
. Th e mos t recen t approac h i s t o carr you t th e oxidatio n t o th e aci d an d esterifi catio n i n on e reactor
. Th e oxidatio n proceed s i n tw o steps
. Th e conversio n o f Ih e secon d methy l grou p i s difficult , bu t mad e easie rb yth e esterificatio n o f th e carboxy l grou p i n p-tolui c acid
. I n thi s continuou s process />-xylen e an d partl y oxidize d produc t ar e introduce d a t Ih e to p ofth e column , an d ai ran d methano l a t th e bottom
. Th e catalys t i s a Cu-M n sai l o f a n organi cacid , th e temperatur e i s I00-200°C , th e pressur e i s 5-2 0 bar
. an d th e residenc e tim e i s 2 2 hours
.

CH , CH ,
CH , CH,O H COOCH ,

COOCH , COOCH , Th e us e o f dimethy l terephthalat e i n thi s proces s i s graduall ybein g displace d b yus e o f terephthali c acid
. Furthe rbackgroun d o n thi s proces s i s give n i n Weisseme l an d Arp e (1978
. pp . 341-44)
. C . Methylamlnes Melhylaminc s ar e prepare d fro m methano l an d ammoni a a t 250-500°C
. A lab oratory-traine d chemis t woul d no t b e abl e t o predic t tha t thi s reactio n woul d pmcce d t o a goo d yiel d usin g thes e raw materials
. Methy l chlorid e woul d b e chosen
. However , b yusin g Ih e appropriat e catalys t (e.g. , aluminu m silicat e at 10-20 0 bar) , ver yhig h selectivit yi s obtained
. CH 3 O H + NH 3 - CHjNH; , + Hj O Th e mono - an d dialkylatio n product s ar c favore d b yexces s ammoni a an d b y additio n o f trimcthylaininc
. Th e worku p consist s o f a pressur e an d a n extractiv e distillation
. Fo rth e latte rtechnique , se e Sectio n 9.1. 1 an d Weisserme l an d Arpe
. (1978
. p . 45)
.P.8 2 

# ST-AF - 00?39/>>/ o 1969 c.3^ ''** 

# 19o 9 DIRECTOR

Y O F CHEMICA L PRODUCER

S UNITE D STATE S O F AMERICA

Informatio n i n thi s Director y i t fo r th o sol o an d prtvat a us

a o f sponsor

s o f th o ^\ig^**at*ftmMSM*^m\*amm\M aWmW

*^^s*\^s\^s*^L\a\Mm*ma\m ^a^Sm^ss\)*t*smm s*\mm\*a*^nma\\ ^Mms^sm**aWtma\%mWt\\ 

### mracrory O

T wnomic M rrooucar s rnjsjwm* 

# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK , N CP.8 3



### 33 3 RAVENSWOO

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A 9402 5 (415 ) 859-362 7 FAX : (415)326-551 2 TWX : 910-373-204 6 TELEX : 33446 6



## S.^S^ir**"" - Un 

## ** Wtt M 

## - " "•»*

——-*.«-« . ea^ma, ,

.*«**»»* ,P.8 4

>RODUCT S , 198 9 DIRECTOR YO F CHEMICA L UNITE D STATE S ormaldehyd e (Formi c aldehyde ) (Methanal ) (Methy l aldehyde ) Methylen e oxide ) (Oxomethane ) (Oxymethylene ) , IOI^
. fcrden Inc
. Borde n Chemica l Divisio n Adhesive s an d Chemical s Divisio n

Perkins Industries , subsidiar y 3orden Chemical s an d Plastic s Partnershi p Demopolis
. Alabam a ^G Diboll
. Texa

s 3 1 Fayetteville
. Nort h Carolin a ~UX> Fremont , Californi a 104 - Kent
. Washingto n V\ L a Grande
. Orego n 3 2 Louisville , Kentuck

yV Missoula , Montan a 4 ( Sheboygan , Wisconsi n &t Springfield
. Orego n M>1 Vicksburg , Mississipp i 2- 1 Geismar, Louisian a 23 6 

# ^w 9

f PRODUCER S 

# *4 - 

# Pf* Annua l Capacit

y (Million s o

f Pounds )



## -ft * 

## re

BT L Specialt yResins Corp
. Chembon d Corporatio n Hampton , Sout h Carolin a 2 3 Houston , Texa

s so Malvern , Arkansa

s 5 Q RndaIusia , Alabam a 3 2 Moncure , Nort h Carolin a 5 ^ Springfield , Orego n 6 3

. Winnfield , Louisiana ' 3 2 P-P2 - P-P l P- PI P-fS . P-P2 ,
0
. B
. Western Ne w Mexic o Adhesives g.l
. d u Pont d e Nemour

s 8 1 Company , Inc
. Chemicals an d Pigment

s Departmen t Virginia , Minnesot a La s Vegas , Ne

wMexic o * 3 P- p 1 \r4fus**-
Belle , Wes

t Virgini a GWMOIII I No

wJoroo y 2i T 102 . Healin g Springs , Nort h Carolin a L a Porte , Texa

s '4 5 Parkersburg , Wes

t Virgini a i? l Toledo , Ohi o ii£ 0VF Corporatio n GA F Chemicals , subsidiar

y Georgia-Pacifi c Corporatio n Chemical Divisio n Calver t City , Kentuck

y Texa s Citv
. Texa

s

Hercule s Incorporate d Operation s Divisio n Hoechs t Ceianes e Corp
. Engineerin g Plastic

s Grou p Hoechs t Ceianes e Chemica l Group , Inc
. Albany , Oreqo n 7 J Columbus , Ohi o IS Conway , Nort h Carolin a <& Crossett , Arkansa

s —7 5 Lufkm , Texa

s K$ Russellville
. Sout h Carolin a ^ t Taylorsville , Mississipp i 22 vio "" a fipnroir*ro , , Louisiana , Missouri i l 

## ?-f l

P-PS
. 

### F-PA P-R 2

Bishop , Texa

s ?* S "Jiirnationa l Mineral s & Chemica l Corporatio n ?itman-Moore , Inc. , subsidiar y Industria l Chemical s Divisio n Newark , Ne w Jerse y5 4 Roc k Hill
. Sout h Carolina? *

^:nsant o Compan

y Monsant o Chemica l Compan

y PVP~Corp T Seiple
. Pennsylvani a 6 1 Chocolat e Bayou , Texa

s O
. Springfield
. Massachusett

s * M brigh t Chemica l Corporatio n •pey.iSS£ - 11^ 8 Citv
. 6reao n t Acme , Nort h Carolin a ~T\\£4<i&*~e. , AlA , S I

» 1 P-P i

P-P2 . P-P I P-? ( P-P i P-P I P-p l P-P i TOTA L Jit . 1 &

50 0 22 5 32 0 40 0 27 5 10 0 10 0 16 0 16 5 10 5 16 5 10 5 21 8 16 0 -125 . 176F>lg O •IOOO ) 1920 12 0 12 0
13 5

Note : Capacities ar

e o n a 37 % basis
. Source : SR I Internationa l estimates a s o f Januar y1 , 1989
. ~fo>J

43o 7 

## T4v ; Formaldehyde-sodiu m bisulfit e adduc t (See : Sodiu m formaldehyde bisulfite ) Formamidin e disulfid e dihydrochlorid e Fran k Enterprises , Inc
. Columbus , Ohi o

SR I Internationa l 

### 87 1P.8 5



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Pvulctct* BptoptU

Subscription

for: Radia n Corporation



# TtteuutdUdltt

Chemical

Products Bo x 23 2 •Cortland , Ne wYor k 1304 5 •(607)753-870 0P.8 6

(ZAtmiCAl

"PXKUCUCU

SuKfeftll * ^ A Reporting Servic e o f r• ~ THenatvttUCHEMICAL PRODUCT S JUN E 198 3 Cortland , Ne w Yor k 13045-023 2 Previou s Report - December198 1 FORMALDEHYD E FOCU S Production o f

formaldehyde in 198 2 amounted t o 4.6 9 billio n pound s (37 % basis ) according to preliminar y dat afro m th e U.S . Internationa

l Trad e Commission . This represent s adeclin e of

18% fro m di e S.72 billio n pounds produce d i n 198 1 an

d i s 26% below th e mos trecen thig h of 6.3 8 billio n pound s turne d ou ti n 1978 . Th

e recor d fo rformaldehyde outputwa

s setin 197 3 whe

n 6. 4 billio n pound s wa

s produced . The declin e in formaldehyde outpu toverth e pastsevera l yearsj s du e principally toth e shar p fal l of f inje w housing constructio n an

d domesti c aul6Tnobde^roducfi61TfF6rirtfiei f mos trecen

tTflgh s reache d i n 1978 . Ne

w housing start

s I n 198 2 T6TalIedT":0

6 millio n units , dow

n 47%Tr6m" the"2.03 mfllTon"unit s starte d inl?7 8 whil e domesti c automobil e production fel l b y 45 % betwee n 197 8 an d 1982 . Th

e larges tuses forformaldehyde , accounting forslightly les s tha n 3/5 o f demand , ar

e i n the manufactur

e of ure a(UF) , pheno

l (PF ) an d melamine (MF ) formaldehyde resin s whic h ar e heavil y dependenton transportation an

d constructio n applications . Buildin g an d construction , an

d relate d end uses , accountfor75-80 % of U F resin consumptio n an

d 70 % o rmor e of P F resi n deman d whil e M

F resin s ar e about50 % dependento n constructio n outlets . U F an d P F resin s ar e widel y used a

s bonding adhesives in th e productio n o f softwoo d plywood , hardwoo d plywood , particleboar

d and fiberglass insulation . Othe rconstructio n relate

d applications ar

e i n decorative laminates an d electrica

l moid* ings . Production o f

particleboard , the larges

toutle tforU

F resins , fel

l by 19 % in 198 2 an

d wa s 36 % below the cyclica

l pea k reache d i n 1978 . Hardwoo

d plywoo d productio n decline d by 11 % i n 198 2 an

d wa s 41 % belo w tha

to f 1978 . Softwoo d ply woo d productio n decline d by 6 % i n 198 2 an

d wa s down by 25 % fro

m the pea

kreache d i n 1978 . The declin e in automobil e production als o impacted o n consumptio n o f P F resin s used in frictio n materials ; foundr y an d shel l moldings ; an

d coate d an

d bonded abrasives . Althoug h th e Consume

rProduct s Safet y Commission (CPSC) banne d th e us e o f

ure aformaldehyde foa

m i n 198 2 a s a n insulation materia

l forhome s an

d schools , the ba

n ha d littl e immediat

e impac ton formadehyde deman d since the advers

e publicit y an d threa to f aba n ha d al l buteliminated the use o f U F foams as a

n insulation materia

l since thi s application peake d in 1977/1978 . OUTLOO KWit

h ne w housing start

s u p substantially i

n th e firs thal f of the yea rto a n annua l rat e of 1.6-1. 7 million units , formaldehyde outpu tshould increase b y 12-15 % i

n 198 3 compare

d to th e depresse

d leve l o f outputin 1982 . I

n the firs tfiv e month s o f

1983 , formaldehyde productio n amounted t o 2.2 5 billio n pounds , o ra ta n annua l rat e o f 5. 4 billio n pounds . I n additio n t o housing starts , automobil e productio n wa s u p b y 25 % i n the firsthal

f o f the year. Wit h interestrates , particularl y formortgages , agai

n approachin

g 14% , iti s unlikely tha tthe curren

tpac e of ne w housing start

s ca n b e sustained forth e balanc e of the year . Overal

l start s will probabl

y en d the yea ra t1.5-1. 6 million unit

s - still asignifican

tincrease compared t o 1982 . Deman d fordomesticall y produce d ne w car s will als o slacke

n i n the second hal

f i f interestrates remai

n a tth e highe

rlevel s forthe res

to f the year . As in th e past, the outioo k fo rformaldehyde i s dependento n prospect s forautomobil e an

d housing . Althoug

h ther e is somewha to f abacklo g of

pentup deman

d forhousing base

d o n populatio n growt

h an d demographics , the prospec to f ne w housing start

s reachin g the 2 millio n unitpe

ryea rleve l in the face of

expecte d hig

h rea l interestrate

s overthe nextsevera

l year s i s unlikely . Automobiles , however , wea rou twit h th e averag

e ag e o f car s o n the roa

d currentl y ove r7 years , u

p fro m 5 year s i n 1978 . Th

e backlog of

deman d fo rne w car s will probabl

y keep automobil e production u p forsevera

l year s compare d to the low level s reache

d a tth e star to f th e decade . I

twill probabl

y tak e severa l year s forformaldehyde production t o excee d th e 6 billio n pound leve

l reache d in 197 3 an

d 197 8 whe

n ne w housing start

s wer e ove r2 millio n units . Th e debat e ove rformaldehyde emission s fro m presse d woo d product

s i s no texpecte d t o be resolve d forsevera

l mor e year s du e t o th e complexity o f th e proble

m compared t o th e U

F foa m case . Th

e recentjudicia

l setbac kagainstth e CPS

C ba n o n ure aformaldehyde foa

m insulatio n will not , however , reviv e th e end use . Woo

d industr y efforts in di e meantime t o mini mize orlessen fugitive emission s fro m presse d woo d products , particularl y particleboard , should diminish th e threa tof a ba n agains tthes e product

s foralon g time. PRICIN G Th

e curren tlis tpric e fo r37 % uninhibited formaldehyde i s 8. 8 cent s pe rpound wit

h actua l selling prices discounted . An

y significan

tincrease i n deman

d and/o rstronge

rselling price

s formethanol , di e feedstock fro m whic h form aldehyd e is made , coul d giv e rise t o increases in actua l an d lis tprices . AVERAG E PRICE S RANG E - FORMALDEHYD

E - 37 % CENT S PE RPOUN D - UNINHIBITE

D - DELIVERE

D - GUL F 196 0 196 5 197 0 197 5 197 9 198 0 198 1 198 2 198 3 198 4 198 5 198 7 Trad e Lis t4. 3 4. 3 3. 5 4. 8 5.4-6. 7 6.7-7. 4 7.4-9. 0 9 8. 8 8.8-9. 3 9. 8 10. 5 Averag e Sales 3 3 2 3 7 7 8 SUPPL Y AN D DEMAN

D Millions o f

Pounds...37 % Basi

s Estimated Domesti c U.S . 196 0 196 5 197 0 197 5 197 9 198 0 198 1 198 2 198 3 198 4 198 5 1987 Capacit y 245 0 348 0 531 5 838 5 887 5 875 0 895 0 869 5 869 5 Production 187 2 310 7 442 7 455 8 597 1 555 5 572 0 469 1 Export s 1 2 1 0 17 12 7 2 0 1 6 1 1 1 0 Deman d 186 0 309 7 441 0 443 1 595 1 553 9 570 9 468 1 540 0 570 0 590 0 630 0 AVAILABILIT

Y Ther

e ar e currently thirteen producer s o f formaldehyde wit

h about5 0 producing units^I n recen t year s th e bul ko f outpu t(68-69% ) wa

s consumed captively fo rth e productio n o f resin s an d othe rderivatrvesTDurin g 198 2 man y formadehyde plant

s wer e shutdown forvaryin

g periods o f

time. Suc h plants , particularl

y thos e closel y tied to facilitie s makin g resi n fo rplywoo d an

d particleboard , ar

e relatively small , an

d shutdown an

d star tu p cost s little . Capacit

y overal l is mor e tha n adequat

e t o satisf y captive an

d merchan

tmarke tdemand . Additiona

l rationalization i s expecte d wit h reduction o f capacit y ove rth e nex tsevera

l years .Hercule s 

### IM C Monsant o Nuodex Rekhhol d Wrigh t 

### 17

0 13 5 69 0 13 0 59 0 8 0 PRODUCER

S AN D CAPACITIE

S - FORMALDEHYD

E - 37 % BASI S - M M LB S PRODUCE

R198 3 CAPACIT Y PRODUCE R198 3 CAPACIT

Y Borde n 157 5 Ceianese 204 0 D u Pont147 0 GA F 25 0 Georgia-Pacifi

c 109 5 Getty-Chembond 41 0 Gul f Oi l 6 0 TOTA L 869 5 Base d o n announced capacitie s an d trad e estimate s withou tallowing forunannounced shutdowns . Atth e end o f 198 2 Reichhol d sol d i tMoncure, N.C . plant , wit h arate d capacit y o f 12 0 millio n pounds , t o th e Chembon d Division o f Gett y Oil . Als o in 1982 , Tenneco sol d its Fords , NJ . plan twit h arate d capacit y o f 13 0 millio n pound s to Nuodex , an d the Garfield , N.J . plant , rate d a t5 5 millio n pounds , t o Kalam aChemica

l along wit

h othe rfacilitie s a

tthos e locations . Nuodex is operating th e Fords plan tbu tth e Garfiel

d formaldehyde unitha

s no tbeen operating . I

n lat e 1981 , Occidenta

l (formerly Hooker) shutdow n a13 5 millio n pound pe ryea rformaldehyde plant . EN D USES The largestend use forformaldehyde , accountin g fo rslighdy les s tha n 1/ 3 o f consumptio n in 1982 , is i n the manufactur

e o f ure aformaldehyd e resins . U F resins ar

e used primaril

y a s bonding adhesives forpresse d woo d product

s suc h a s plywoo d an

d particleboard , wit

h particleboar

d application s dominating , taking about75-80 % o f U F resi n outpu tan

d plywoo d 8-10% . Otheruse s fo rU F resins ar

e in protectiv e coatings . Pheno l formaldehyde (PF ) resins ar e the second larges

t use , accountin g fo rabout1/ 5 o f formaldehyd e consumption . Th e larges tuses forP

F resin s ar e a s adhesives forplywood , particleboar

d an d fiberglass insulation , whic h accountfo rabou t2/3 o f consumption . Othe

ruses forP

F resin s ar e i n molding compounds , laminating , frictio n materials , abrasive s an d coatings . Melamin

e formaldehyd e (MF ) resins , arelatively smal l outlet , ar e used in molding compounds , decorative laminates , dinnerware , coatings , pape ran d textil e treatments . Reactio n o f

formaldehyde wit

h acetaldehyd e gives pentaerythritoi whic h i s used t o mak

e alkyd resins , explosives , syntheti c lubricants , an

d multifunctional monomers . Formaldehyde is polymerized to giv e polyacetal resin

s whic h ar e molded into engineering plasti c part s fo rappliances , consumerproducts , plumbing an d hardware, an

d industria

l an d automotive products . Reactio n o f

formaldehyd e wit

h acetylen e gives 1,4-butyne diol whic h i s hydrogenated t o 1,4 butan e diol , (1,4-BD) . 1,4-BD i s used t o mak

e polybutylen e terephthalat e plastics butits majo

rus e i s in th e manufactur e o f tetrahydrofura

n (THF) . Polyvinyl pyrrolidone i s als o mad e fro m fro m 1,4-BD vi

athe intermediat

e butyrolactone . Reactio n o f formaldehyd e wit

h ammoniayield s hexamethylenetetramin e whic h i s used primaril

y t o cur e phenoli c molding compounds . I tals o ha s us e in the manufactur

e o f chelatin g agents , explosives , an d bactericides . EN D USE PATTER

N - 198 2 ESTIMAT

E DERIVATIV

E PERCEN T Ure aFormaldehyde Resins 3 1 Phenol Formaldehyde Resins 2 2 Melamin e Formaldehyde Resins 4 Pentaerythritoi 9 1,4-Butane Diol 9 Aceta l Resins 8 Hexamethylenetetramine 6 Methy l Diphenyl Diisocyanate s 2 Miscellaneous 9 MANUFACTURIN

G Formaldehyd e i s mad e fro m methanol b y tw o processes ; th e silvercatalyzed proces s wher e formaldehyde i s mad

e b y acombinatio n dehydrogenation-oxklatio n proces s an d th e meta

l oxid e proces s wher

e methanol is oxidize d directl y t o formaldehyde . I n th e silvercatalyze d process , vaporized methanol , togethe rwit h ai ran d stea m preheated t o 100 ° C , is passe

d overathi n bed o f

silver-crysta

l catalyst . Formaldehyde is forme d by dehydrogenatio n o f

methanol . The reactio n i s endothermi c an d require s hea twhic h is provide

d by burnin

g tiie hydrogen produced in th e dehydrogenatio n reaction . The exi tgases ar e quenche d and condense d t o produce amethanol-formaldehyd e solution . Th e methanoli c formali

n fro m the absorberca

n b e th e fina

l produc to rels e i ti s distille d t o lowe rmethanol conten tt o 1 % orless . Th e meta l oxid e proces s involves th e oxidatio n o f methanol overacatalys to f molybdenum an

d iro n oxide . Th

e reactorconsists o f

amultipl e tub e uni tfilled with catalys tan d havin g ahea ttransfe rfluid aroun

d th e tubes . A mixtur

e of ai ran d methanol ar

e vaporized an

d passe d int o th e tubes . Temperature s ar e o n di e orde

ro f 300 ° C . Th

e reaction is highl

y exothermi c an

d hea tgenerated provides stea m fo rus e by le tdown turbines t o driv e pump s an

d to provide proces s heating . Th e effluentgases ar

e fe d directl y t o a

n absorptio n tower . Demineralized wate ri s fed a tth e to p o f

th e towe ran

d formalde hyd e solutio n i s collecte d a tth e bottom . ENVIRONMENTA

L ASPECT

S Formaldehyd e i s toxi c by inhalation , prolonged o rrepeated contac twit h th e ski n ormucou s membranes , an d by ingestion . I

ti s extremel y irritating to th e eyes , nos e an d throa to n exposure to concentration s rangin g fro m 0. 1 t o 5 ppm . The OSH A exposure limi ti s currently 2 pp m fo ra n eigh thou

rtime weighte d averag

e bu tachang e t o 1 pp m has been proposed . Formaldehyd e i s asuspected carcinogen based o n demonstratio n o f carcinogenesi s in animals . I twas foun d t o caus e nasa l cancer s i n rat s afterexposure to 1 5 pp m fo r13-1 6 months . Epidemiologica l studie s o f

plan t worker s b y Ceianese an

d D u Pontreveale

d n o unusua

l incidenc e o f

cancer . T o th e bes to f

ourknowledg e th e informatio n containe d herein i s accurate . However, w e d o no tassume an

y liabilit y whatso everforth e completenes s oraccurac y o f thi s report.«

•. , i * 

# CHEMICA L PROFIL E FORMALDEHYD E Septembe r 18,198 9 

## SUPPL Y PRODUCE R CAPACITY * Alcolac , Seiple , P a 13 5 Borde n (1 2 sites ) 2,27 6 BT L ( 3 sites ) 28 5 Chembon d ( 4 sites ) 40 0 D.B . Wester n ( 2 sites ) 9 0 Degussa , Theodore , Al a 6 5 D u Pon t ( 5 sites ) 1,45 0 GA F ( 2 sites ) 20 0 Georgia-Pacifi c ( 8 sites ) 1,46 5 Hercules , Louisiana , M o 18 0 Hoechs t Ceianese , ( 3 sites ) 2,06 0 Monsanto , ( 2 sites ) 47 5 RVP , Whit e City , Or e 30 0 Wright , Acme , N C •11 4 Tota l 9,49 5 'Million s o

f pound s annuall y o n a 3 7 percen t basis . D u Pon t close d its Grasselli , N.J. , plan t a t th e en d o

f 1988 , an d plan s t o mov e th e equipmen t t o it s L a Porte , Tex. , sit e b

y th e en d o

f nex t year , t o suppl y th e company' s BDO facility . Th e mov e wil l mea n a n extr a 20 0 millio n pound s o f capacity a t La Porte , wher e capacity wa s expande d b y 3 0 millio n pound s last year . Th e compan y starte d a ne wplan t a t Parkersburg , W . Va. , i n th e fourt h quarte r o

f las t year . Monsant o close d it s Addyston , Ohio , plan t at th e en d o f 1987 , an d wil l be expandin g its two remainin g plant s b y th e en d o

f thi s year , fo r a n additio n o

f abou t 2 0 millio n pounds . Georgia-Pacifi c increase d capacity a t seve n o f it s plants , mostl y i n th e firs t quarte r o f thi s year , fo r a tota l increas e o f 12 0 millio n pounds . Th e compan y i s considerin g buildin g a ne wplan t a t Grayling , Mich . Chem bon d intend s t o rais e capacity a t Springfield , Ore. , b y 10 0 millio n pounds , to 30 0 million , b

y th e firs t quarte r o

f 1990 . Hoechst Ceianes e plan s t o boost capacity a t Bishop , Tex. , b

y 10 0 millio n pounds , t o 1. 9 billion , b y th e en d o

f thi s year . Borde n debottlenecke d seve n o f it s plant s fro m th e en d o f 198 8 t o th e firs t quarte r o f thi s year . Th e compan y acquire d Perkin s Industries ' 60-million-poun d plan t i n 1987 . Deguss a entere d th e formaldehyd e busines s whe n i t opene d its plan t last year . Alcola c i s a subsidiar

y o f Interche m Inc. , whic h acquire d IMC' s formaldehyd e an d othe r Industria l chemica l businesse s las t April . Profil e las t publishe d 9/29/86 ; thi s revision , 9/18/89 . DEMAN D 1988 : 6.7 3 billio n pounds ; 1989 : 6. 5 billio n pounds ; 1993 : 7. 6 billio n pounds . (Include s export s bu t no t imports , bot h of whic h ar e negligible . Las t year , export s totale d 1 9 millio n pounds , an d import s totale d 1 1 millio n pounds.) . GROWT H Historica l (1979-1988) : 0. 4 percen t pe r year ; future : 2. 5 t o 3 percen t pe r yea r throug h 1993 . PRIC E Historica l (1952-1989) : High , 10.5c . pe r pound , 3 7 percen t basis , uninhib ited , f.o.b . Gulf ; low , 3c . pe r pound , tanks , dlvd . Current : 9.8c . t o 10.5c . pe r pound , f.o.b . Gulf . USE S Urea-formaldehyd e resins , 2 5 percent ; phenoli c resins , 2 2 percent ; acetyleni c Continued o n Pag e 4 7« ^ 

# 1 CHEMICA L PROFIL E FORMALDEHYD E Septembe r18.198 9 Continue d fro m Pag e 54 chemicals , 1 1 percent ; poryaceta l resins , 9 percent ; pentaerythritoi , 7 percent ; hexamine , 6 percent ; urea-formaldehyd e concentrates , 6 percent ; MDI , 5 per cent ; melamin e resins , 4 percent ; miscellaneous , 5 percent
. 

### STRENGT H Polyaceta l resin s ar e growin g a t 5 percen t o rgreate rpe ryear . Acetylenic s ar e growin g nearl ya s much , le d b y1, 4 butanedio l us e i n PB T an d THF
. 

### WEAKNES S Export s o f finishe d woo d product s ar e dow n thi s year , resultin g i n les s deman d fo rU- F an d phenoli cresins
. Small , direct-applicatio n use s o f formalde hyd e hav e bee n pron e t o substitution , du e t o safet yconcerns . 

### OUTLOO K Overal l growt h wil l no t excee d 3 o r4 percent
. Shoul d th e econom yfalte ran d constructio n decline , deman d fo rformaldehyde-containin g resin s wil l slacke n further
. Formaldehyd e remain s a highly-scrutinize d chemica l amon g regulatory agencies , an d futur e actio n agains t i t i s a possibility
.