OAR Box 1867 

Prepped by Ollie Stewart 

Document Number: 

9) ll-B-63 

Docket Number: 

A-90-19 

Printed 12/2/2008 6:27:19 AM Sheet 9 of 9 5 

p.1 
P.2 

A-90-19 

II B 63 

MEMORANDU M 

TO: 

FROM: 

DATE: 

SUBJECT: 

Process Vents Docket A-90-19 

Wanda Floyd 

December 1990 i 

HON NESHAP: Industry Characteristics/FormaldjhyBPA AIR DQCK E 

••— • TM"iini i n in M 

I l SEP . il 

r?i 

\rj 

Attached is a product-process summary (PPS) for the production of Formaldehyde 

via Dehydrogenation of Methanol and Formaldehyde via Air Oxidation of Methanol 

category. This PPS was developed as part of the Industrial Profile project in 

support of the Hazardous Organic NESHAP (HON) regulatory effort. Information 

in this PPS is used as a basis for emissions and cost impact estimates for the 

HON program. 

Listed below are the key references used in developing the attached PPS. 

"Formaldehyde." In: Chemical Marketing Reporter. Schnell Publishing 

Company, Inc., New York, September 18, 1989. 

1989 Directory of Chemical Producers USA. SRI International, California. 

p. 671. 

"Formaldehyde." In: Mannsville Chemical Products. New York, June 1983. 

White, Howard. Introduction to Industrial Chemistry. John Wiley & Sons, New 

York. pp. 106-107. 

EPA-450/3-80-028d. Organic Chemical Manufacturing. Volume 9: Selected 

Processes. December 1980. 

Weissermel, Klaus and Arpe, Hans-Jurgen. Industrial Organic Chemistry. 

Verlag Chemie, New York, 1978. pp. 34-37. 

Chenier, Philip, Jr. Survey of Industrial Chemistry. John Wiley & Sons, New 

York, 1986. pp. 208-209. 

Shreve, R. Norris and Brink, Jr., Joseph A. Chemical Process Industries. 

4th edition. McGraw-Hill Book Company, New York, 1977. p. 598. 

x Document is Docket Item , 

A-90-19 

ll-B-252 

cao.067 

formald 
P.3 

JSfev. 

Preparer: f*?^ ^ai]toJ< 

Oate: ' t- 9o 

Reviewer: 

Product-Proem CM« 

ADMINISTRATIVE NOTES 

^oooo ft 

*•* +z.o lfn/'°rt Hours spent on this PPS 

p.p Nam e fer^alJeLjU Pr*~ ^^<^i , / / H,^/ ^ C 

Incomplete Items (parts of 

form you cannot complete) 

Mine # and description) 

\£IM, > r><'*>*' SoW L-LJ»~ •'/•* ,/"'3 -

Date Cleared Initials 

7//7/J* # 

QA4 

7/ lff/«W 

# 

Chemicals mlsslno CAS numbers 

Plant with C1tv but no Countv (plant name, city , state) 

$0rJe» c/U^/c^li 4 pl*sfci 

•3. ... c tfe«H* 
P.4 

Chemical Name 

Reviewer 

PRODUCT-PROCESS SUMMARY (PPS) 

^<rriA^A^^LuAp . 

Preparer: ^/V^Xx^ -

Date: 7//?/9^> 

Alternative Chemical Kaaw 

CAS I SO OOO 

Karen Floler CftemlcaT Number 

CHEMICAL SPECIFIC INFORMATION 

1.0 U.S. Production 

-pcnrnJ-o ^Id&kMobLr 

12£_ 

Ref # A ., Pg # ., Ref Year /ffl 

(indicate the same reference information for any answers below from a 

different reference) 

I.I Urrfts o f production (circle one1(fmj]2jonsofjjt^ o r millions of gallons 

l.f V.S> Cecity —- » ^ 5 ,o6 4-3 0~7 '^^3o i .o«* 

1.3 U, & C^acHy Ut1Tf|f|§|| 

1.5 Imports 

1.6 Exports 

1.7 Product Price 

1.7,1 Average Price O.ZZ. 

O.CV 

Z<»39 

1 

\,&0 /o6 /is 

£-.0 

S,6 

I.7.Z Of»1t$ of price ^rcT#«ie)/^oS) r S/qallon « 

•pricfc.-f.a.b, £(j £ 

1.8 Comments 

CW*~«U /<?<}£-tf£- WZ0) /o'*& 

2<13<? - 5 *• ?.& 
P.5 

>2. 0 Chenlcal End-Use Ref # ^" . Pg I _ , Ref Year ^^^ 

USI — Percent 

Poll«Cet*L ^S/nS 

Pe>,t«erjtlr>toL 

"I 

-i'6 

s7 
3.0 U.S. Producers Ref # •*• \ °\ . Pg # , Ref Year jTO ^ i ^ 

P^iilli^ f prtftfl&M J*!*&*?»«) (^—minion ? of gaiion? 

3.2 Nane, Location, and Capacity 

Location, 

ggtty, C*tf«*t*f Process Used Capacity , , 

m

^ MM ("se P-P #) Units* IO6 k g 

5az. ctMfl-cl<*a£>l. 

Total Capacity 43<3~7 
P.7 

>RODUCTS 

1 989 DIRECTORY OF CHEMICAL 

UNITED STATES 

__ pPRODUCERS 

pormaldehyd e (Formic aldehyde) (Methanal) (Methyl aldehyde) 

Methylene oxide) (Oxomethane) (Oxymethylene) t 

fcrdenlnc. n ^Smm ^£lfc* 

Borden Chemical Division

 u 

Adhesives and Chemicals Division .jOtmopous. Alabama % 

*OiScWTexas... 31 >• 

Feyettevil!e,.North Carolina 3flOj 

Ff«m6nt,:Galifornia 104 - , f 

Kent, Washington' ~~~~ 

La Grande, Oregon 

Louisville, Kentucky 

Missoula, Montana 

Sheboygan, Wisconsin 

Springfield, Oregon M>' 

vickr - "'

 : Perkins - Industries, subsidiary 

garden Chemicals and Plastics 

Partnership 

, Mississippi 

Gaianar, Louisiana 

(TL Specialty Resins Corp. 

Chembond Corporation 

0. B. Western 

New Mexico Adhesives 

g. I. du Pont de Nemours & Company, 

Inc 

Chemicals and Pigments 

Department 

Hampton, South Carolina 25 

Houston, Texas So 

Malvern, Arkansas So 

Anaaiusia, Alabama 3 2 

Moncure, North Carolina 5 4 

Springfield, Oregon 63 

Winnrield, Louisiana 32. 

Virginia, Minnesota 

P-F2. 

Annual Capacity 

(Millions of Pounds) 

-ee* ss 

11 u u / 

90 

ISO 

240 

-&**• (*0 

520 

—TLT 

110 

110 

I* 

Las Vegas. New Mexico xSi.' p. **" , p \r4V»**-

Betfa, Wen Virginia 

w-Joraoy 

0VF Corporation 

GAF Chemicals, subsidiary 

&•?» 

j Now Jorooy 

Healing Springs, North Id ' 

Carolina* 

La Porte, Texas '45 

Pirkersburg, West Virginia r?l 

Toledo, Ohw ixg-*> 

?-fl 

Georgia-Pacific Corporation 

Chemical Division 

Calvert City, Kentucky 

TMM ftp/ TpfMS 

45 

45 

Hercules Incorporated 

Operations Division 

Albany, Oregon "7J 

Columbus, Ohio IS 

Conway, North Carolina 4 $ 

Crossett, Arkansas^ rSm— 

Lufkin, Texas 4 f 

Russellville, South Carolina W 

Taylorsville, Mississippi TS 

Wi^"rn fifimrjii *** 

Hoechst ceianese Corp. 

Engineering Plastics Group 

Hoechst Ceianese Chemical Group, 

Inc. 

Louisiana, Missouri- tl 

Bishop, Texas W 5 * 

$4rrtstionai Minerals & Chemical 

Corporation 

Pitman-Moore, Inc., subsidiary 

Industrial Chemicals Division 

Newark, New Jersey 54 

Rock Hill. South CarolinaS4 

*{onsanto Company 

Monsanto Chemical Company 

fVPCoro. 

Seipla^Pswwsytwtia t l 

Wright Chemical Corporation 

Note: Capacities are on a 37% basis. 

*texas"*fc* 

lusetts Q4 » 

qe Citv. Oregon, 

8& ~ Immmntifcinm 

p-Pap-PS. 

?-PI 

w i 

•p-pa. 

?-?i 

TOTAL 

« 

120 

140 

70 

40 

50 

500 

225 

320 

400 

J 7 5 

100 

100 

160 

165 

105 

165 

105 

218 

160 

105 

170>>lgO 

•1000) 1920 

120 

120 

135 

Source: SRI International estimates as of January 1, 1989. 14*5 

Formaldehyde-sodium bisulfite adduct (See: Sodium 

formaldehyde bisulfite) 

Formamidine disulfide dihydrochloride 

Frank Enterprises, Inc. Columbus, Ohio 

SRI International 671 
P.8 

4-J>o7 

PRODUCT-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) 

ih« <\o ifi 

Ref * } - Pg # ^ <**' 

Commercially % Nat'l 

Viable, (Y/nl Capacity 

p.p 2fl>»V 6lt**{*fr"' * / ~<-fLc,»ot 

P-P 3 ; 

P-P 4 

P-P 5 • 

P-P 6 ' 

4.1 Documentation of P-Ps Excluded 

P-P not 

Cwrorclillv yiibli 

/ 27 ^ 

Reasons 

/^r^aloleljh ^°^ "*"]<!• toj€**fc*n * / **tH***l 
P.9 

Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenation Reaction 

Condensation Reaction 

rTOefiydrogenatlon Reaction, 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydrofortnylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenatlon Reaction 

Sulfonatlon Reaction 

Catalytic Reformation 

Hydrod1mer1zat1on Reaction 

10 ^ 

Ref # , Pg I 

Generic Reaction 

4.4 ExpUIn how you selected the reaction type 1n line 4.3. 

as 
P.10 

4.5 Written Description %>£ * <&> P^,# (Hst^otl) ^ ' 

de^ito!^9 1"'

 indiCate references « * P«9t "umbers throughout written 

\-o -<T>rt*v WvJ-tS; "T ^ *»ofcbU(i'c/ -Stfj/ V dclt|«{rcn^U*****- fort«*/*XUO— |^>x^^ _ 

Ws*^o|^c^ *•**- e*.c^< *>f \*aAk*^4l /C*A-A. **&**-*[ L<r^(j&Jhr*flV*£ Ktri. *JL*\^. 

-ttuu. C^p \crl<As€s rtrUr*£Jlr . 

v*4w fufihw, p»n~s U*ru, x. Itrit* <v tr*oe*.Urs A f *-

- TU ^r^j^J ^ /.y*U c~;,^ .f U^J4^cL W 

( ( ~=~wU W i^rt j ^ ^ J t 5 £ ^ v ^ *£ ^lu^^, fire. Aj 
P.11 

KO ',* <UcUA io **-i+4&r f^Wr> U 4W %h*ro^c c^tUfl^, 

Zrtr^AA&Lq**,/ /M-efk* ^ UfoCtAiJy^iifK pAJ^V 4Q tt**fjfl+*0r 

5.0 Process Flow Diagram (attach at end of package) 

5.1 Flow Diagram Reference: Ref # 20 Pg # ~&tf*vhl ; Pt'f.M'l 

5.2 Comments on Flow Diagram 

VwaaeA plih^Jr cltc^a > 

5.3 Process Components Ref # 2o Pg # Re^i ; 

Component Tvoes EflUfefifc CP^tTtero i f tiOtie '''^"- i 

shewn) 

Distillation ColumnsfV«'«^-<» *fi^Wa| \ 

Absorbers nc^e^ J 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

o*\^" ^i^iU -fr>u>eir 

X 

c*n~j>re*.<zor _J 

^ " ^ c , | (,W ) -1 T#u l ^^j , _ ^ 
P.12 

6.0 Chemical Data 

6.1 Balanced Chemical Reactions Ref # \Q \ A# . pg # 3S /g^v-i ) 

6.2 Chemical Tree Ref , ^ Pg # _^ 

kh ^ — l •s^g '

 Jtk*W*»^; ^rv^M^U 
P.13 

6.4 , Stolchlometry Ref # Pa # 

Show calculations and assumptions and then summarize 1n table on next 

page. 

/GW* 30,03) 

U ^ try, X ^ s4 ^ r> K „ , ^H* ^ o f W ^

 ; 

n . ^ 

t^ole, 

t^l * Cr/,0 * <*3 ^ ^ fl 

* A 07 

* * 

/•x~>k CM7O -2L, ^ 

^ Ox . 33,3 We ^ 2 0, H^lf i y#fltt 

*7 

Hip-. 

f — • o :

 A /0/f A- ,, „ 
P.14 

6.4.1 Product 

6.4.2 Raw MateriaUs) 

#1 ^*AMNXA*4>\ 

#2 

#3 

#4 

#5 

§,4-3 Co-ProdMCts 

#i 

#2 

#3 

H 

#5 

6.4.4 Bv-Products 

#1 KvO . 

#2 

#3 

#4 

#5 

6.4.5 Intermediates 

#1 

#2 

5b ooo 

Q15&1 1,01 

wo dean 0*G>0 
_PJf 

6.4 Stolchlometry Conversion Factors 

fl,fg 

b) @||||i*f0i>;ms*r foi* Cfr>ProducCfI 

c) Conversion factor for Co«Product I I 

d) Cww^ttttJFjMttf fotr Co-Product 13 

e) Conversion Factor % c&flrotf&ct M 

f) Conversion Factor Comments 

^ T*e£ ^ ^0 , &^*H- ± j R^f ^ fO , pj 3£ j 
P.16 

7.0 Process Vent Emission Sources 

7:1 \mmBBm*** «•* **»*•*? / <Y/N) 

7.2- *i r Oxidation vent esrtsstans? K/ (Y/N) Ref # , Pg # 

7.3 Comments Ref # , Pg # 

7.4 Reactor vent emissions? V (Y/N) Ref # J£ , Pg # jfe^rf 1 • 

7.5 Comments Ref i I ***/&> / Pg # 
P.17 

mt. •*!**«* * -£- (Y/N) Ref # ££__, Pg # f^rrfX, 

Ref # l*hf±J_, Pg I 

I K oJ*X\^iv*~ 4~* W4,c. "^»*-civKP<TV>-/ 

CrJoSttfrlxtrrS , 
P.18 

8.0 Transfer Emission Sources Ref # 2-0 pg # Raj»#rf i 

0.1 l l AlrF\M^ts/€^Pros<fects Transferred? V (Y/N) 

8.2 What ilterials are transferred? 

8.2.1 Product 

8.2.2 Co-Products 

8.3 Comments Ref # , Pg # 
P.19 

9.0 Storage Emission Sources Ref # 2® » Pg # ^ar f 

9.1 Are riH&Tt- stored? ^ (Y/N) 

9.2 What materials are stored? 

Storage Service 

i

 TyPe 

9.2.1 Product 

9.2.2 Co-Products 

9.2.3 Raw Materials 

4^jejk\AOJVKe\ Q15QI @) neAqcle. v*Mir 

9,2.4 Intermediates 

9.4 Comments 
P.20 

10.0. Wastewater Emission Sources Ref # 10 Pg # ?&ftrrfl j 

10.J r$"fl^Rt#r"p^$«lt? Y (Y/N) ^Jt-i -

10.2 Describe wastewater 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

#1 3.' chsorlvr ~~ Hi.* vr?l -fWr^ nu\- o.&o (£*. / l.oi^ powW-

#2 VKC. 4r/U^TUr>ja^>~ Q^Ltu^- * - Col. i/vutlu-efg^ l-t«>±Uvij Cei'l-s « fk***^ O^*/*. 

#3 IV K a^e-U»^A>ev^ (~okJ. <y* spudt~ s*4HJ 

. Ifffizci^r.. i^fJ^Tf^l... 5*1 .hyt^tif. J***Jy*L% Jbvl* 

10.3 Stream Composition Ref # , Pg # 

(provide only if readily available) 

Stream #1 Steam #2 

Organics Organics 

HAPs HAPs 

Water (O /*0 fc^ +• , .) Water 

Other Other 
P.21 

Stream #3 

Organics _ 

HAPs 

Water 

Other 

10.4 Comments Ref # 2-0 Pg # \Uf**+± 
P.22 

A 

Preparer: 

Date: 

Reviewer: 

. . /*e.U; ^7,loi. 

f -io 

Product-Process Code 

ADMINISTRATIVE NOTES 

T0 (LQ T/rtfr6) Hours spent on this PPS 

P-P Name F%*m*Mtlylt . ht^pf./Wfa a / t,tfUMj 

Incomplete Items (parts of 

form you cannot complete) 

(line * and description) 

(\w»&) 

->'.•. S^.j. " •7-^T 

m? ha 

Initials 

Chemicals missino CAS numbers 

Plant with C1tv but no Countv (plant name, dty , state) 

Sec p(a/*ofr l^^l Sect. 3,2- .^> T — Y J C^.J,J, , ,iO-
P.23 

Preparer: ^/IOJUJUDate: if i vfln 

Reviewer: 

Chemical 

PRODUCT-PROCESS SUMMARY (PPS) 

^oTiA^aejjLjAp „ 

Al ternative CfteuJictT Name 

CASjP SO OOO 

CHEMICAL SPECIFIC INFORMATION 

1.0 U.S. Production 

-pprnJ-c *-ldeJr*Md&~ 

±2X_ 

Ref # A ., Pg * ., Ref Year I&I 

(Indicate the same reference information for any answers below from a 

different reference) 

IV! ° fcjrcle onelTmTnions ofkcT^or millions of gallons 

1.3 , U;,.MCallc:nrUI|TUa,tidii 

1.7 Product Price 

I.7^^verag||||l:|i 

ivr.z optifo 

17773 ^Ca 

4-301 

0. 6? 

1131 

5>0 

$.6 

0,2-X ^_i»0L- a,2lb 

l b

 * ^ r

$/7cTor S/oallon ° 

<\4^5 io6 (bs* 430 7 '0*fc<9 

or f$4? l°

6

^k 

ptrodtA^f^ « d«^A»ws/ - iLp#Ws 

+ -*0<spe>cf-S 

2^39 - 5 v- ?.£ 

- 2144.6 10* <* 

yrica, ,-A.a.b, CiJ^ 

1.8 Comments 
P.24 

2.0 Chenlcal End-Use Ref # . Pg # _ , R9f Year HI ^ 

W Percent 

\Jrax -fowUdjh "V-S ^5/ 

Pe»t^erjt^'toL 

"hi *U„i*.*o reS,\,$ 

K • . -

/VS c- 7 

9'/ 

Hi 

s'6 
P.25 

J

 <3

~ 

n> « e >• 

IA 

**-

-P> 

IA S. 0) 

o 

3 

"*? 

O 

k 

</» f > 

>» • J 

o 

1 

u 

e CM 

JR 

0 ) . V» I 

IAQ. 0> U 0) O IA W 3 

0.">— 

utmxm 

s 

r 

^ 

v 

f 

r 

a (J 

o 
P.26 

1989 DIRECTORY OF CHEMICAL PRODUCERS 

-.ROOUCTS UNITED STATES hf^^ 

(Formic aldehyde) (Methanal) (Methyl aldehyde) 

' Methylene oxide) (Oxomethane) (Oxymethylene) 

"JTiW'" 

'Borden Chemical Division 

Adhesives and Chemicals Division Demopolis. Alabama 3fo 

Diboll, Texas 3«t 

Fayetteville, North Carolina lOb 

Fremont, California 104 -

Kent. Washington- n 

La Grande. Oregon *% 

Louisville, Kentucky V 

Missoula. Montana 4L 

1ifr*tf 

r 

Perkins Industries, subsidiary 

•MKCBBmicals and Plastics 

Partnership, 

Sheboygan, Wisconsin * t 

Springneld. Oregon 

_ Geismar. Louisiana 2Zi 

Hampton, South Carolina 23 

P-PI 

p-ez. 

New Mexico Adhesives 

£.1. du Pootoe Nemours & company, 

Inc 

Chemicals and Pigments 

Department 

Virginia, Minnesota If" 

Las Vegas. New Mexico a s 

P-P ^

P-P: i w~* 

Virginia 

Owsaallii Hew Jowey 

Healing Springs, North 103. 

Carolina 

La Porte. Texas '45 

Parkersburg, West Virginia rf I 

Toledo, Ohio ^ 

?-fl 

HarcuBa Incorporated 

Operations Division 

ftoaeW CelaneW Corp. 

Engineering Plastics Group 

Hoechst Ceianese Chemical Group, 

Inc 

IMmational Minerals K Cnerngjti 

Corporation 

Pitman-Moore, Inc. subsidiary 

Industrial Chemicals Division 

Louisiana, Missouri tl 

Bishop, Texas ?*5 

4>nsintsCompany 

Monsanto Chemical Company 

Seipte. Pennsylvania 61 

Chocolate Bayou, Texas **• 

Springfield. Massachusetts Q 4 

IWPCam. 

fltigtt Oienfical Corporation Acme, North Carolina 61 

Note: Capacities are on a 37% basis. 

Source: SRI International estimates as of January 1, 1989 

P-PI 

?-Pi 

P-PSL 

P-P2. 

?-P« 

P-Pl 

•p-fa. 

p-fl 

P-PI 

TOTAL 

T5*\i 4307 

Annual Capacity 

(Millions of Pounds) 

-- . to 

3H?tt?o 

- ^ * * 

90 

ISO 

240 

S20 -

110 

110 

120 

140 

70 

40 

__S0 

500 

170i>lgO 

•tooo» ieao 

120 

120 

14^5 

Formaldehyde-sodium bisulfite adduct (See: Sodium 

formaldehyde bisulfite) 

Formamidine disulfide dihydrochloride 

Frank Enterprises, Inc Columbus, Ohio 

SRI International 671 
P.27 

PRODUCT-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) 

\ Name . 

Ref I low 7^;)W/ 

P-P 3 

P-P 4 

P-P 5 

P-P 6 

4.1 Docunentatlon of P-Ps Excluded 

p.p not " 

Conmerclallv Viable 

Commercially % Nat'l 

Ylable (Y/n) Capacity 

r 27 ^ 

Reason? 

F^r^alJiehll* - IT^»- «j r arJdochioy^ " •j- **tHa*»L 
P.28 

4.3 SifcTft en»I 

d Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenatlon Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenatlon Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenatlon Reaction 

Sulfonatlon Reaction 

Catalytic Reformation 

Hydrodlmerizatlon Reaction 

Ref I 

(o 

Pg * 

1* 

Generic Reaction 

4.4 Explain how you selected the reaction type in line 4.3. 

^ ,t«w ;+ iit /*A*»** 
P.29 

u4.5 Written Description 

denscHpl?of!;:argin'

 ind1Cat e reference s and

 P^e numbers throughout written 

A portion of the air is passed through the vaporizer column, where it is saturated 

with methanol (Stream 2). The methanol-saturated air is then mixed with the regaining air and preheated by heat exchange with the product gas leaving the converter. 

The feed gas mixture (Stream 3) then enters the converter. Conversion ratios of 

97% are obtained. The converter, heated by the exothermic oxidation reaction, is 

**>-0 maintained at 345°C (ref. 5) by boiling heat transfer fluid in the reactor shell. 

Steam is generated by condensation of the heat-transfer fluid vapors. 

The product gas (Stream 4) is cooled by heat exchange with the feed gas mixture 

and then quenched in the absorber column. The formaldehyde and methanol are removed from the gas stream by absorption in the aqueous solution. The unabsorbed 

gases and vapors exit at the top of the absorber column. A portion (60 to 80%) 

of this gas is recycled (Stream 5) and the remaining gas is vented. The product 
P.30 

solution drawn from the bottom of the absorber column contains approximately 0.8% 

Mthanol and 0.005% formic acid. The solution is usually treated in an ion exchange 

system to 'reduce the acidity and is then stored. As a final step water is added 

to provide a suitable concentration for storage and shipping. Process yields of 

1,5 

91 to 93% are reported for the metal-oxide-catalyst process. 

The formaldehyde yield from the metal-oxide-catalyst process is higher than that 

from the metallic-silver-catalyst process and the metal-oxide-catalyst process is 

simpler, because methanol distillation is not required. The equipment costs for 

the metal-oxide-catalyst process are greater because of the large volume gas 

streams; also, because of a lower concentration of formaldehyde in the product 

gas stream, the absorber column diameter is larger and the operating temperature 

is lower than those used with the metallic-silver-catalyst process. 

5.0 

5.1 

5.2 

Process Flow Diagram (attach at end of package) FiaTR"^ 

Flow Diagram Reference: Ref # _£ 0 , Pg #fyz^*r+l 

Comments on Flow Diagram 

5,$ Process 

Component Types 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

£<n+^r*4Sor' 

k*-iy-&r-~ 

trX*" lVDU$ U, •fVvi/« _ I 

h4*Jr -e^.ei*ji*^Aey- _ \ 

\Oy*. e^Gk&s\~ajuT - ' 

Total 

Ref # i£__ , Pg # B*$*r±J~ 

0 

-fc. 

J2. 

/ 

pN)t zero ff hone 

shown) 

fi^TB-'Z 
P.31 

6.0 Chemical Data 

6.1 Balanced Chemical Reactions Ref # >° pg # 

6.2 Chemical Tree Ref ; /o Pg # ^ 

/*/<„./ _ * '

 gxA/ ' - ^ ^jiA.U 
P.32 

6.4 Stolchlometry Ref # ' & pg # ^ * 

Show calculations and assumptions and then summarize 1n table on next 

page. 

uo _ ^ pcflo + tti ° 

31 + U > ^ + ' 

6\, 
P.33 

6.4 StolchlOMtry Conversion Factors 

a) 

b) 

0,°il 

for <r$H*ooMF« 

c) Mtrsiocfsctw m t&mmtrn 

d) Conversion Factor for Co-Product 13 

s S V V*f V****** S N *+****M+^J*VAr*****'*V*V r***r\ f N V NS f* A ^ 

e) Conversion Factor for Co-Product 14 

f) Conversion Factor Comments 

r^f *20j XL^^I) 
P.34 

6.4.1 Product 

F*r*<tJ*hJ* 

6.4.2 Raw Material(s) 

n 

#3 

#4 

#5 

0 400 

& v 

6.4.3 Co-Products 

#1 

#2 

#3 

#4 

#5 

6.4.4 Bv-Products 

#1 

n 

#3 

#4 

#5 

\J-«ft f 

H£*-

A"-*<77—s^TT" 

6.4.5 Intermediates 

#1 

#2 

M 

Q- $ 

TTSaiftS 6 
P.35 

7.0 Process Vent Emission Sources 

7,2 Aircs^ili^venl J»f$slonsf V (Y/N) Ref # , Pg # 

7.3 Comments Ref # 24 Pg # &f*r+ l 

Air •>'«! K*cfc> e***??^!/^ 4o ir^clirJI^ '. 

_ ir\.o ofi'st-i'll^Ht^ 4 » > 

7.4 Reactor vent emissions? N/ (Y/N) Ref # , Pg # 

7.5 Comments Ref # , Pg # _ 
P.36 

\?w®mm M (Y/N) Ref # ., Pg # 

vacuum 

Ref I ., Pg # 
P.37 

8.0* Transfer Emission Sources Ref # ^ Pg # R^-jftyrfi-

*•* »i9HHr^ ^ v7 (Y/N) 

8.2 ' tWligi$M***re fransfentedf 

8-2.| Product 

•forvwlA-ei«~u\Qr2^ So OOP 

8.2.2 Co-Products 

8.3 Comments Ref # , Pg # 
P.38 

9.0 Storage Emission Sources 

9\I Are materials stored? Y (Y/N) 

9.2 What materials are stored? 

Ref I , Pg # . 

Name 

9-2,1 Product 

£arf*i*(J*L<iJl ^ 

9.2.2 Co-Products 

9.2.3 Raw Materials 

Xu 

Storage Service 

Type 

S^4f***0 

(fte+rkU) 

pr<rXJ41$61 s?9r*jt %Jl •/rtbw-mibH 

sia^^^- #-r*~ ?!., I — 

9.4 Comments 

0\Ur sVr^juijA 
P.39 

10.0. Wastewater Emission Sources Ref # f ° Pg # 

10.1 ft wafffctater- pre$e»tt / fY/Nl *> / K*f*mrl 

10.2 Describe wastewater r^M-Ji llrflOj^ 

Stream Equipment Component 

Number Producing Wastewater ^. JK6lu^l^»/5^0flwents on ^ o w 

, . , J^i) ^"th »«*-f//, Ok* Ur^l4tLH 

/ $ #2 i^p^r.-t^^ K^SI^AX) - ^ci^J^s h&4i^ <&k o*«-*L s*Ufi^ psOAjJier^ 

§3 SUA, <*sa*k +crUsf>A*> ~ S pt*<k co^^hc-

..jttlf. lQ^.t<£d*AirAfVC. riiVJ^.-^-.^i^tA*^-? 

10.3 Stream Composition Ref # , Pg # 

(provide only 1f readily available) 

Stream #1 . j Steam #2 

7,/) -7MA 

Organics Organics 

HAPs HAPs 

Water (O^O k^ f-,.l Water 

Other Other 
P.40 

Stream #3 

Organics _ 

HAPs 

Water 

Other 

10.4 Comments Re f # xo , Pg # JW+l. 

1A 
I i 

METHAtJOl. 

STORAGE 

CAUSTIC WATER 

AIR 

@ - STORAGE EMISSIONS 

?) - WAUDUV4G, EMI^blOUS 

tj) - FUGITIVE EMlVblOWS -

OVERAUL PI.AUT 

® - SECOWDAR-f EMISbtOU POTEWT 

I 

u» 

PRODUCT 

STORAGE 

^ PRODUCT 

( W-Ci") FRACTIOUATIOM 

Fig. III-l . Flow Diagram for Uncontrolled Model Plant Producing Formaldehyde from 

Methanol with the Metallic-Silver-Catalyst Process 
P.42 

SH-3?7 

fourth edition 

CHEMICAL 

PROCESS 

INDUSTRIES 

R. MORRIS SHREVE 

Lata Prof—or Emaritmt of ChomUeaJ EagimaaHng 

Purdaa Lnivtnily 

JOSEPH A. BRINK, JR. 

Conutldng OumUmi Eagim—r 

Prof—or and Chairman of Ckamicmi Engimaarlng 

faMngtom Stmto VnimnHy 

NcCRAW-HIU. BOOK COMPANY 

Sam I M *. IM * Sam flmli n Aaama 

.VavlMU Panama 

ST*—f Taara Tm 

rarlt Saaramm 

RADIAN LIBRARY 

DURHAM, N. a 
Umnrwot Cttaiogtagfai Data 

Shrew, Rudolph Norris. 188S-1975. 

Chemical process industries. 

Includes bibliographies tod index. 

1. ttemistry. Technical. I. Brink. Joeeph A., 

date, joint tudior. II. Tide.. 

TP145.S5 1977 660.2 77-4236 

ISBN 0-07-057145-7 

Copyright © 1977. 1967, 1956 by McCrtw-Hill, Inc. All rights 

Copyright 1945 by McCftw-Hill, Inc All rights reserved. 

Printed in the United States of America. No part of this 

publication may be reproduced, stored in s retrieval system, 

or transmitted, in any form or by any means, electronic 

mechanical, photocopying, recording, or otherwise, widnut . 

die prior written permission of die publisher. 

34567890 FGRFGR 7865432109 

Tha editon for OOM book won Jeremy Robinson and Either Gettm, 

and the production supervisor wot fossa F. Leaden. 

It wot set in Bodomi Book. 

Printed and bound by Fairftetd Graphics. 
P.44 

>\Ave. • \U 4 < .,.1-

598 [Chap. 34) Plastic Industries 

Dilute caustic. 

LSAir I 

_ scrubber tir—Q—*\\ 

Ottgoses 

Preheoter 

y Compressor Steam Filter 

/""*\ Methanol 

S'Ort jrlrLj—f* (ra) 

Supemeoter 

*^teom 

A 

> 

Converter Primory . i 

I I absorber 

W 

Vaporizer 

Steam 

+&• 

Steam 

condensate 

Secondary 

absorber 

info 

ft3f 

V' 

rtz 

^ 

flMoken 

U tank \J 

Lsr^ 

Recycle methanol 

Fig. 34.8 Flowchart tor the manufacture ot' formaldehyde. 

If two molecules of acid react, a compound such as ethylidene diacetate is formed: 

The newer method, however, is to start with ethylene and by oxychlorination (dehydrochlorinationi 

obtain apparently a cheaper procedure for.linvl chloride.** See Fig. 34.9. which presents a Howchafor the following reactions: 

Chlorination 

CjH4 + Q2 —-»QH^ j 

DichloroethyleQe 

Oxychlorination 

CjH, + J02 + 2HQ -^ » CjH4a2 + H20 

Dehydrochlorination 

cricking furnace. 

c*HA "^a~-< C2H3Q + HQ 

tad pretiun 

Dichloroethyleiie Vinyl chloride 

The CuQ2 catalyst (on an inert fixed carrier) may react as follows: 

CjH4 4- 2CuOj • CjH ^ + Cu-jClj 

CujClj + JO, • CuO • Cudj 

CuO • CuQj + 2HQ • 2CuQ2 + H20 

4>Edwarda and Weaver. New Route to Vinyl Chloride. Chem. Eng. Prog.. 61(1). 21 (1965) (prescribed costs relative to 

process starting with ethylene); Burke and Miller. Oxychlorination, Chem. Week, Aug. 22. 1964. p. 93 (excellent overall commercial and technical presentation and patents); Riegel et at.. Low Cost Hydrocarbon Chlorination. Chtm. Eng. Prog.. 69(10). 

89 (1973). 

/ 

C'ONVE 

OCE

 : 

OXYCHLORIN ' 

'fig. 34.9 F! 

HCI .= 

7312-H. 102 • 

PHTH, 

the establisl 

many plasti 

mines, erytl 

facturina ar 

(Chap. 39). 

able prices, 

expanded t; 

plasticizers 

The pt 

thalene wht 

to carbon d 

ing phthalii 

Btu/lb of r 

Oxide 

agent is ail 

"ECT. ; 

"Phthali 

Eng. (.V. Y.). : 
P.45 

Survey of 

Industrial Chemistry 

Philip J. Chenier 

Professor 

Department of Chemistry 

University of Wisconsin-Eau Claire 

Eau Claire, Wisconsin 

A Wiley-Interscience Publication 

JOHN WILEY & SONS 

New York • Chichester • Brisbane Toronto • Singapore 
P.46 

-vi- ' 

208 Chemicals from Methane 

0 

II 

Formaldehyde, H-C-H ; Methanal 

References 

I. & M. pp. 422-429 

CP. 9-26-83 

KC. 2-4-85 

Formaldehyde is produced solely from methanol. The process can be air 

oxidation or simple dehydrogenation. Various metal oxides are used as 

catalysts. Temperatures range from 450-90()°C and a short contact time of 

0.01 sec. Formaldehyde is stable only in water solution, commonlv 37-5ficj 

formaldehyde by weight. Methanol (3-15%) may be present as a stabilizer. 

Formaldehyde in the pure form is a gas with a bp of -21°C but is unstable 

and readily trimerizes to trioxane or polymerizes to paraformaldehyde. 

oxidation 2CH3OH + 0 2 — 

dehydrogenation CH3OH

 A

 » 

a- CH2 = O + 2H_>0 

CHo = O + Ho 

r-i 

trioxane 

H0-(CH2-0)-H 

n 

n = 8-50 

paraformaldehyde 

Uses of Formaldehyde 

Urea-formaldehvcle resins 

Phenol-formaldehvde resins 

Pentaervthritol 

Hexameihvlenetetramine (HMTA) 

Urea-formaldehvde concentration 

Polvacetals 

1.4-butanediol 

Melamine-formaldehyde resins 

MDI 

25<7C 

20 

7 

7 

6 

5 

5 

4 

4 

Two important thermosetting plastics, urea- and phenol-copolymers, 

take nearly one half the formaldehyde manufactured. 1,4-Butanediol is 

made for some polyesters and is an example of acetylene chemistry that has 

not yet been replaced. 

pentaeryth 

tetranitratt 

tondensa t 

\tetalcleh\ 

coiidensuti' 

(ormaldefr 

O 

II 

C H 3 - C -

Hexamet 

nolic resin i 

Although it 

condensatio 

Debate is 

products, e 

construction 

TLV of for 

irritant and 

Consumer P 

insulation, iv 

T h e final si 

carcinogen." 
>n>cess can be air 

\ides are used as 

ut contact time of 

• mmonlv M-ji')c/r 

ent as a stabilizer. 

'C but is unstable 

iformaklehyde. 

+ 2H 2 0 

H-, 

nol-copolymers. 

i .4-Butanediol is 

hemistrv that has 

Methanol. CH3OH; Wood Alcohol. Methyl Alcohol 209 

HC^CH + 2CH,0 

HO-CH,-C=C-CHo-OH 2H, *. HO-CH2 -CHo-CH2 -CH2 -OH 

Pentaervthritol finds end-uses in polyesters and explosives (pentaervthritol 

tetranitrate). To appreciate this synthesis, the student should review two 

condensation reactions, the crossed aldol and the crossed Canizzarro. 

Acetaldehvde reacts with 3 mol of formaldehyde in three successive aldol 

condensations. This product then undergoes a Canizzarro reaction with 

formaldehyde. 

O 

II 

CH3-C-H + 3CHoO OH 

OH 

I 

CHo o 

-s- HO-CH 2 -C-C- H -£££. 

| OH" 

CH2 

I 

OH 

C(CH2OH)4 + HCOOH 

pentaerythritol 

Hexamethylenetetramine (HMTA) has important uses in modifying phenolic resin manufacture and is an intermediate in explosive manufacture. 

Although it is a complex three-dimensional structure, it is easily made by the 

condensation of formaldehyde and ammonia. 

CH20 A mj ,Nh 6 H2O 

Debate is continuing on the safety and toxicity of formaldehyde and its 

products, especially urea-formaldehyde foam used as insulation in 

construction and phenol-formaldehyde as a plywood adhesive. Presently the 

TLV of formaldehyde is 2. Conflicting studies of formaldehyde as an 

irritant and possible carcinogen abound in the literature. Although the 

Consumer Product Safety Commission banned urea formaldehyde foam 

insulation, in 1983 a U.S. Circuit Court of Appeals overturned this decision. 

The final story is still to be written. Formaldehyde is now a "suspect 

carcinogen." 
Klaus Weissermel 

Hans-Jiirgen Arpe 

Industrial 

Organic Chemistry 

Important 

Raw Materials and 

Intermediates 

Translated by 

Alexander Mullen 

Verlag Chemie • Weinheim • New York 

1978 
P.49 

Prof. Dr. Klaus Weissermel 

Dr. Hans-Jiirgen Arpe 

Hoechst AG 

Postfach 800320 

D-6230 Frankfurt 80 

West Germany 

Preface 

Copy Editing: Dr. Hans F. Ebel 

This book contains 43 Tables 

CIP-Kurztitelaufnahme der Deuischen Bibliothek 

Weissermel. Klaus 

Industrial organic chemistry: important raw 

materials and intermediates'/ Klaus Weissermel; 

Hans-Jiirgen Arpe. - l.Aufl. - Weinheim, New York: Verlag Chemie, 1978. 

Dt. Ausg. u.d.T.: Weissermel. Klaus: Industrielle organische Chemie. 

ISBN 3-527-25706-3 (Weinheim) 

ISBN 0-89573-005-7 (New York) 

NE: Arpe, Hans-Jiirgen: 

© Verlag Chemie GmbH, D-6940 Weinheim, 1978 

All rights reserved (including those of translation into foreign languages). No part of this book may be reproduced in 

any form - by photoprint, microfilm, or any other means - nor transmitted or translated into a machine language 

without written permission from the publishers. 

Registered names, trademarks, etc. used in this book, even without specific indication thereof, are not to be considered 

unprotected by law. 

Printer: Passavia Druckerei GmbH Passau 

Printed in West Germany 

Industrial organic cr 

as well as, to an inci 

present status of kn 

There was thus a gr< 

and intermediates c 

and to present it in i 

development, which 

from their industrial 

ing discussions with 

This book addresse 

from it the chemisti 

manufacturing proc 

glean information a 

and feedstocks alor 

disciplines in the cl 

economists - will b 

economic interrelat 

This book is arrang 

their tightest possit 

unavoidable. The ii 

As a rule, the manu 

ment and significa; 

applications of the r 

products are frequ* 

existing technologic 

more economic or i 

The authors endea* 

information are at • 

1. The main text. 

2. The synopsis of I 

3. Flow diagrams il 

These three types o 

or making brief no 

notes which briefly 

to be rapidly inforr 
\r>-h34 2. Basic Products of Industrial Syntheses 

Hoechsl-Uhde 

Mitsubishi Gas Chemical 

Shell 

at planning stage: 

Dor Chemicals. Israel 

feed, other companies such as Hoechst-Uhde, Shell, Mitsubishi 

Gas Chemical and Dor Chemicals in Israel either operate or are 

planning pilot plants with methanol as substrate. 

In 

be 

commercial forms of HCHO: 

1. hydrate, HCHO H: 0 

HO-CH,-OH 

H-K>CH2^OH 

>i < 10 

tnoxan Cf^ o 

3. paraformaldehyde 

H-f-OCH,-r;OH" 

'M > 10 

HCHO feedstocks: 

1. CHjOK approx. 92% share 

2. C,-Ci alkanes, approx. 8% share 

3. (CHJOCHJ) 

HCHO production (in 

1974 

USA 0.98 

W. Germany 0.50 

Japan 0.37 

million t): 

1975 

0.77 

0.40 

0.31 

1976 

0.69 

0.49 

0.38 

HCHO manufacture from CH3OH according to two principles: 

I dehydrogenation or oxydehydrogenation 

with Ag or Cu 

2. oxidation with MoOj + Fe;03 

characteristic differences because of explosion range for CH,OH/air between 

2.3.2. Formaldehyde 

At room temperature, formaldehyde is a colorless gas which 

readily polymerizes in the presence of minute amounts of impurities. Therefore, there are three commercial forms usually 

available in place of the monomer: 

l.The aqueous 35-55% solution in which formaldehyde is 

present to over 99% as the hydrate or as a mixture of oxymethylene glycol oligomers. 

2. The cyclic trimeric form called trioxan obtained from the acid 

catalyzed reaction of formaldehyde. 

3. The polymer form of formaldehyde called paraformaldehyde 

which results from the evaporation of aqueous formaldehyde 

solution and which can be reversibly converted to the monomer by the action of heat or acid. 

The processes for manufacturing formaldehyde are based essentially on methanol.and the light hydrocarbons (methane to 

butane) as feedstocks. 

Methanol has developed from the first commercially operated 

dehydrogenation in 1888, to the currently dominating source of 

formaldehyde. Only_in_ the USA, a small amount of forma):, 

dehyde (approx. 8% of world production) is manufactured, via 

radical oxidation of light hydrocarbons. Besides these, the 

oxidation of dimethyl ether is also of some importance. 

The available production figures for formaldehyde in several 

important industrial countries are listed in the adjacent table. 

2.3.2.1. Formaldehyde from Methanol 

Formaldehyde can be manufactured from methanol via two 

basically different reaction routes: 

1. Dehydrogenation or oxidative dehydrogenation in the presence of Ag or Cu catalysts. 

2. Oxidation in the presence of Fe-containing Mo03 catalysts. 

The oxidative dehydrogenation process with Ag or Cu metal is 

operated above the explosion limit with a small quantity of air. 

.A 

d 

ll 

tl 

V' 

a 

I 
•\A » A 

2.3. C,-Units '35 

P.51 

e. Shell, Mitsubishi 

ither operate or are 

:rate. 

olorless gas which 

ite amounts of imrcial forms usually 

1 formaldehyde is 

a mixture of oxv-

|n the oxidation process, a small amount of methanol is reacted 

helow the explosion limit with a large excess of air. 

To I: 

Aa catalysts (crystals or nets) are preferentially employed in the 

detndrogenation and oxidative dehydrogenation of methanol, 

[n the BASF. Degussa, Du Pont, ICI and Monsanto processes 

the catalyst is arranged as a few centimeter thick layer in the 

reactor. In the CdF Chimie process, silver is used together with 

a carborundum support. 

In the initial step methanol is dehydrogenated: 

to I: 

small amount of 0 :. i.e. CH3OH content 

>36.5 vol.-*/: 

to 2: 

0 ; excess, i.e. CH3OH content <6.7 vo\.-r> 

1. HCHO manufacture w'aCHjOH dehydrogenation or oxydehydrogenation 

catalyst mainly employed in three forms: 

1. 0.5-3 mm crystals 

2. nets 

3. impregnated on SiC 

lined from the acid 

paraformaldehyde 

ous formaldehyde 

.•rted to the monoivde are based es-

'bons (methane to 

nercially operated 

minating source of 

mount of formalmanufactured via 

besides these, the 

mportance. 

dehyde in several 

ie adjacent table. 

lethanol via two 

nation in the preg Mo03 catalysts. 

AgorCu metal is 

all quantity of air. 

CHjOH ^ HCHO + H2 UH •• 20 kcal, .> 

+

 84U

 /mo 1 (15) 

Hydrogen can be combusted exothermally on addition of air 

/ A LI -

 5 8 kca l 

Thus the following formal equation results for the oxidative 

dehydrogenation: 

moll 

CH3OH + 0.5O2 - HCHO + H20 

' *\H 38 kcal 

159U /mol (16) 

A less than stoichiometrical amount of air is employed in the 

industrial process. The air is fed so that the reaction temperature remains constant (±5°C) in the range 600-720°C. However, at temperatures between approx. 600-650°C there is an 

incomplete methanol conversion necessitating a recycle. On 

adding H20 at 680-720°C there is almost complete conversion 

of the methanol in a single pass. The water has another favorable effect on the life of the Ag catalyst in that the steam delays 

the deactivation caused by sintering of the thin layer of silver 

crystals during the weak red heat. The catalyst has a life time of 

2-4 months and the spent catalyst can be easily regenerated 

electrolytically without loss of Ag. The catalyst is sensitive to 

traces of other metals as well as halogens and sulfur. 

The hot gases from the reaction are very quickly cooled to 

approx. 150°C and washed in a counterflow with H20 in several 

mechanism of oxidative dehydrogenation: 

primary dehvdrogenation on metallic Ag or 

Cu 

secondary H-. combustion with Oprocess characteristics: 

control of oxidation via O, feed (adiabatic 

method) without external heat supply or removal at 600-720°C. i.e. Ag red heat 

H: 0 addition has several effects: 

1. increases CH3OH conversion 

2. interferes with Ag recrystallization 

3. lowers the C deposition on Ag surfaces 

therefore, increase in life of catalyst 

Ag reactivation via electrolytic regeneration: 

Ag dissolved at anode and deposited at 

cathode 

thermal decomposition of HCHO to 

CO + H2 is suppressed through: 
\JJ -i" 'H36 2. Basic Products of Industrial Syntheses 

1. short residence time at thin catalyst layer 

2. rapid cooling (0.1-0.3 s) to I50°C 

2. HCHO manufacture via CH3OH oxidation: 

catalyzed by metal oxides based on 

Fe:OrMoO,. possibly with Cr,03 or CoO 

as promoters 

effective catalyst: 

Fe(Mo04)3 sensitive to heat due to M0O3 

discharge. Excess Mo03 replenishes losses 

and avoids drop in activity 

process characteristics of the oxidative 

HCHO manufacture: 

advantages: 

1. low temperature reduces material 

problems 

2. higher HCHO concentration attainable 

directly without subsequent distillation 

disadvantages: 

great excess of air means higher investment 

and energy costs compared to Ag process, 

waste gas with HCHO non-combustible and 

requires special HCHO removal treatment 

life time determined by mechanical stability 

of the catalyst pellets 

absorption stages. The solution is stabilized towards polymerization with a residual amount of methanol (l-2wt.-%). A 

distillation can be connected in order- to produce concentrated 

formaldehyde solutions (37 to 42 wt.-%). The yield of formaldehyde is 87.5%-and the selectivity* reaches 91%. i.e. It 

formaldehyde requires 1.22 t of methanol. 

The by-products are CO and CO:. There is virtually no formic 

acid present. 

To 2: 

In the oxidation process, the formaldehyde formation occurs 

practically as a pure methanol oxidation (eq. 16). A mixture of 

18-19 wt.-% Fe,03 and 81-82 wt.-% Mo03 is employed as 

catalyst. Under carefully controlled conditions, it is converted 

into the catalytically active iron(III)-molybdate. 

Excess M0O3 is frequently added in order to make up for losses 

resulting from formation of molybdenum blue. This compound 

goes to the cooler end of the catalyst bed and simultaneously 

lowers the catalytic activity and selectivity. Cr- and Co-oxjde 

can be used as promoters. 

In the industrial process, methanol vapor, together with a large 

excess of air at 350-450°C, is led over the catalyst in a tubular 

reactor. The heat of reaction is removed by a liquid which 

surrounds the tubes. After cooling to 100°C the gases from the 

reaction are scrubbed with H:0 in a bubble column. By adjusting the amount of water, the concentration of the formaldehyde 

solution can be varied between 37 and 60 wt.-%. The methanol 

conversion is roughly 95-99% and the formaldehyde selectivity reaches 91-94^ ; 

The by-products are CO, CO, and formic acid. The latter can be 

removed in a coupled ion-exchanger. 

The life time of the catalyst is roughly two years. The PerstorpReichhold ("Formox'), Hiag-Lurgi, Montecantini, SBA, 

IFP-CdF, and Lummus processes were developed in accordance with this principle. 

Dimethyl ether is employed in a similar manner to methanol for 

oxidation to formaldehyde. 

Be 

tru 

L'U 

M: 

of 

t u i 

of 

pr. 

de 

tin 

ut. 

sol 

va 

an 

m; 

\V 

US' 

nu 

Fu 

as 

7 

tic 

M. 

bu 

4.-

pr. 

*) c.f. Definitions of Conversion, Selectivity and Yield, Section 15.2. 
P.53 

*J 'fir 

2.3. CrlJnits 37 

.•d towards polymeritnol (l-2wt.-%). A 

•roduce concentrated 

The yield of formal-

.-aches 91%. i.e. It 

is virtually no formic 

de formation occurs 

,»q. 16). A mixture of 

lo03 is employed as 

tions. it is converted 

bdate. 

to make up for losses 

nlue. This compound 

I and simultaneously 

y. Cr- and Co-oxide 

together with a large 

: catalyst in a tubular 

d by a liquid which 

'C the gases from the 

e column. Byadjustof the formaldehyde 

•vt.-%. The methanol 

maldehvdeselectivicid. The latter can be 

\ears. The Perstorpontecantini. SBA, 

.•veloped in accordmer to methanol for 

2.3.2.2. Formaldehyde from Other Products 

Besides the two main manufacturing routes based on methanol 

ihere are a few less important processes employing other precursors. 

Many companies have been working on the selective oxidation 

of CH4. However, the low rate of reaction of CH., at temperatures below 600 °C coupled with the high rate of decomposition 

of formaldehyde above 600°C have meant that no industrial 

process has been developed to date. Decomposition of formaldehyde could only be avoided by extremely short residence 

times. A Hiils process has recently been described involving 

partial oxidation of methane to methanol and formaldehyde. 

The residence time and pressure were 1.55 x 10"3sand60bar, 

respectively. 

In the Ceianese oxidation process involving propane or propane-butane mixtures, formaldehyde and acetaldehyde are 

formed in the gas phase along with numerous other oxidation 

products. 

This process is described in connection with acetaldehyde manufacture {c.f Section 7.3.2). 

2.3.2.3. Uses of Formaldehyde 

Apart from the direct aprjHcjitjons of aqueous formaldehyde 

solutions (Formalin®, Forrnol®^ e.g. as disinfecjant_and preservative. and as arfauxiliary agent in the textile, leather, fur. paper 

and wood industries, most of the formaldehyde is used for resin 

manufacture with phenols, urea and melamine. 

Water-free pure formaldehyde or its trimer (trioxan) can be 

used to manufacture high molecular thermoplastics (polyoxymethylene). 

Furthermore, the synthetic pathway to polyhydric alcohols such 

as pentaerythritoi, trimethylolpropane and neopentyl glycol 

(c.f Section 8.3) is opened up by formaldehyde Waco-aldolization. 

Moreover, formaldehyde is employed in the manufacture of 

butynediol according to Reppe (c.f. Section 4.3), of isoprene via 

4,4-dimethyl-l,3-dioxane (c.f. Section 5.2.2), and of fJpropiolactone (c.f. Section 11.1.7.1). 

HCHO manufacture from light hydrocarbons: 

I.CH4 

- C3HS.CjHu, 

to I: 

CH4 oxidation with Hiils process (not on 

industrial scale up to now) avoids HCHO 

decomposition at the high temperature level 

necessary by extremely short residence 

times 

to 2: 

C3H„.'C4H,0 - Ceianese process for oxidation used industrially in USA 

HCHO only in mixture with other producHCHO applications: 

1. formaldehyde condensation products 

(thermosetting plastics) 

2. trioxan for polyoxymethylene 

3. aldol reactions: 

pentaerythritoi, trimethylolpropane. 

neopentyl glycol 

4. butynediol manufacture: 

HOCH,CaCCH,OH 

5. various, among others: 

HJC 

H3C O-' 

ield. Section 15.2. CfH,C-CHCOOH 
P.54 

dEFtt 

United States 

Environmental Protection 

Agency 

Office of Air Quality 

Planning and Standards 

Research Triangle Park NC 27711 

TLS 

EPA-450/3-80-028d 

December 1980 

Air 

Organic Chemical 

Manufacturing 

Volume 9: Selected 

Processes 
P.55 

1-i 

t' V\°l 

REPORT 1 

FORMALDEHYDE 

R. J. Lovell 

IT Enviroscience 

9041 Executive Park Drive 

Knoxville, Tennessee 37923 

Prepared for 

Emission Standards and Engineering Division 

Office of Air Quality Planning and Standards 

ENVIRONMENTAL PROTECTION AGENCY 

Research Triangle Park, North Carolina 

December 1980 

This report contains certain information which has been extracted from the 

Chemical Economics Handbook, Stanford Research Institute. Wherever used, it 

has been so noted. The proprietary data rights which reside with Stanford 

Research Institute must be recognized with any use of this material. 

D2R 
• ta» * • ia •MilJamda^lMIMBMITHIaMMMliTM 

1-ii i 

CONTENTS OF REPORT 1 

I. ABBREVIATIONS AND CONVERSION FACTORS 

II. 

III. 

IV. 

INDUSTRY DESCRIPTION 

A. Reason for Selection 

B. Formaldehyde Usage and Growth 

C. Domestic Producers 

D. References 

PROCESS DESCRIPTION 

A. Introduction 

B. Metallic-Silver-Catalyst Process 

C. Metal-Oxide-Catalyst Process 

D. Other Processes 

E. References 

EMISSIONS 

A. 

B. 

Formaldehyde from Methanol Process Using a Metallic 

Silver Catalyst 

Formaldehyde from Methanol Process Using a Metal 

Oxide Catalyst 

C. References 

V. APPLICABLE CONTROL SYSTEMS 

A. Formaldehyde from Methanol Process Using a Metallic 

Silver Catalyst 

B. Formaldehyde from Methanol Process Using a Metal 

Oxide Catalyst 

C. References 

VI. IMPACT ANALYSIS 

A. Environmental and Energy Impacts 

B. Control Cost Impact 

C. References. 

Pacre 

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-12 

V-l 

V-l 

V-5 

V-9 

VI-1 

VI-1 

VI-4 

VI-21 

VII. SUMMARY VII-1 
II-l 

II. INDUSTRY DESCRIPTION 

A. REASON FOR SELECTION 

Formaldehyde production was selected for study because preliminary estimates 

indicated that emissions of volatile organic compounds (VOC) from the industry 

were high and because an increase in formaldehyde consumption was expected to 

continue. 

Pure, dry formaldehyde is a colorless gas characterized by a pungent odor. Its 

stability in the gaseous state depends on its purity; however, even traces of 

water will cause rapid polymerization. Therefore formaldehyde is manufactured 

and transported only in solution or in the polymerized state. The domestic 

production capacity of formaldehyde is reported traditionally on the basis of a 

37 wt % solution, although it is manufactured and sold in different forms, e.g., 

37, 44, 50, 52, and 56 wt % solutions and as paraformaldehyde, a solid. Wher 

ever possible customers buy the high-concentration product in order to reduce 

freighl 

dehyde. 

37, 44, 50, 52, and 56 wt % solutions and as paraformaldehyde, a solid. When1S1 

freight charges. Appendix A gives the pertinent physical properties of formalB. FORMALDEHYDE USAGE AND GROWTH 

The current production capacity of formaldehyde in the United States (based on 

37 wt % solution) is 4066 Gg/yr, with the 1977 production being 2750 Gg/yr, or 

1 2 68% of this capacity. ' Formaldehyde consumption is expected to increase at an 

average annual rate of 4 to 5% during 1977—1982. ' At these rates production 

will be 85%;pf current capacity by 1982. 

The uses of formaldehyde and their expected growth rates are given in Table II-l. 

The manufacture of adhesives constitutes 60% of the end use for the formaldehyde 

produced. The major derivatives -- urea-formaldehyde and phenol-formaldehyde 

resins — are used principally in the manufacture of particle board and plywood. 

Thus the consumption pattern of formaldehyde depends largely on the construction 

industry. 

The manufacture of plastics accounts for approximately 10% of the formaldehyde 

produced. Butanediol, a derivative of formaldehyde, is used in making polybutylene terephthalate (PBT). If the use of plastic in automobile production increases 
II-3 

and PBT plastic is chosen as the principal material used, formaldehyde could have 

a growth rate of more than 10% annually for a few years. 

DOMESTIC PRODUCERS 

Because most of the formaldehyde is manufactured and shipped as a solution containing 50% or more water, the distance from the producing point to the consuming 

point is minimized to reduce shipping costs. Therefore the industry is characterized by a large number of relatively small plants. Since more than half the 

formaldehyde used is in the manufacture of adhesives for wood products, the 

3 

producing plants are located predominantly in the south and northwest. 

Sixteen producers were operating 55 formaldehyde plants at the end of 1977. 

Table II-2 lists the producers, locations, capacities, and processes; Fig. II-l 

shows the plant locations. 

Formaldehyde has a tendency to polymerize on storage. When an inhibitor is added 

to prevent excessive polymerization at lower storage temperatures, it is usually 

methanol at 7 to 11% concentration. Most of the formaldehyde is sold uninhibited 

and must be kept warm (above 54°C) to prevent polymerization. 

All the formaldehyde produced in the United States is made from methanol either 

by a combination oxidation-dehydrogenation process using a silver catalyst or by 

catalytic oxidation in the vapor phase using a metal oxide catalyst. About half 

the formaldehyde producers also produce methanol feedstock (Borden, Ceianese, Du 

Pont, Georgia-Pacific, Hercules, IMC, Monsanto, and Tenneco). Reichhold is the 

only large producer that does not make its own methanol feedstock. 
! 

II-4 

Table II-2. Formaldehyde Capacity 

Capacity0 (Gg/yr) 

Location Silver. Metal Oxide 

Key Producer Process Process 

Allied Chemical Corporation 

IA South Point, OH 141 

45 

36 

106 

113 

36 

59 

102 

36 

29 

41 

109 

( ckk/.jd rt7t^y.ff--Hfr\) (_ -~t id txkt^y^. ~) 

2A 

2B 

2C 

2D 

2E 

2F 

2G 

2H 

21 

2J 

2K 

3A 

3B 

3C 

4A 

4B 

5A 

5B 

5C 

5D 

5E 

Borden, Inc. 

Demopolis, AL 

Diboll, TX 

Fayetteville, NC 

Geismar, LA 

Louisville, KY 

Sheboygan, WI 

Fremont, CA 

Kent, WA 

LaGrande, OR 

Missoula, MT 

Springfield, OR 

Ceianese Chemical Company 

Bishop, TX 

Newark, NJ 

Rock Hill, SC 

Chembond Corporation 

Springfield, OR 

Winnfield, LA 

Du Pont Company 

Belle, WV 

LaPorte, TX 

Healing Springs, NC 

Linden, NJ 

Toledo, OH 

Georgia-Pacific Corporation 

7A 

7B 

7C 

7D 

7E 

7F 

7G 

7H 

Albany, OR 

Columbus, OH 

Coos Bay, OR 

Crossett, AR 

Russellville, SC 

Taylorsville, MS 

Vienna, GA 

Lufkin, TX 

680 

45 

53 

53 

68 

32 

GAF Corporation 

6A Calvert City, KY 45 

54 

45g 

4lg 

45 27 

.13 

54 

113g 

45 

Gulf Oil Corporation 

8A Vicksburg, MS 27 

Hercules Inc. 

9A Louisiana, MO 77 

9B Wilmington, NC 45 

Hooker Chemicals and Plastics Inc. 

10A North Tonawanda, NY 61 

riHi 

227 

145 

100 

73 i 

122 I 

i 
P.60 

II-5 

Table II-2. (Continued) 

Location 

Key 

14E 

14F 

14G 

14H 

15A 

15B 

16A 

Producer 

IMC Chemical Group, Inc. 

Moncure, NC 

Tacoma, WA 

Tuscaloosa, AL 

White City, OR 

Tenneco Inc. 

Fords, NJ 

Garfield, NJ 

Wright Chemical Corporation 

Reigelwood, NC 

Total process capacity 

Number of plants 

Percent of total industry capacity 

Capacity of total industry 

Capacity (Gg/yr) 

Silver 

Process 

11A 

11B 

12A 

12B 

12C 

12D 

13A 

14A 

14B 

14C 

14D 

Seiple, PA 

Sterlington, LA 

Monsanto Corporation 

Addyston, OH 

Chocolate Bayou, TX 

Eugene, OR 

Springfield, MA 

Pacific Resins & Chemicals, Inc. 

Eugene, OR 

Reichhold Chemicals, Inc. 

Hampton, SC 

Houston, TX 

Kansas City, KA 

Malvern, AR 

29 

14 

45 

88 

45 

134 

43 

23 

23 

33 

45 

45 

3040 

35 

74.8 

Metal Oxide 

Process 

54 

50 

55 

22 

113 

39 

1026 

20 

25.2 

4066 

aSee refs. 1 and 2. See Fig. II-l for plant locations. Because of space 

limitations, symbols on map do not reflect precise locations. Based on 37 wt % 

solution. Silver catalyst process. Mixed metal-oxide-catalyst .process. 

Capacity of Russellville, SC, plant, which came on-stream in 1975, is 113 Gg/yr 

[see 1976 Directory of Chemical Producers. United States of America, p. 62 in 

January to July Supplement, Chemical Information Services, Stanford Research 

Institute, Menlo Park, CA (July 1977)].

 gGeorgia-Pacific Corporation in 1979 

stated their Columbus, Coos Bay, and Russellville capacities to be 32, 34, and 

90 Gg/yr (per letter dated May 30, 1979, from V. J. Tretter, Georgia-Pacific, to 

R. T. Walsh, EPA). In 1976 Rohm and Haas closed an 11-Gg/yr plant at Philadelphia, PA, and Union Carbide closed a 54-Gg/yr plant at Bound Brook, NJ. 
P.61 

III-l 

mm 

III. PROCESS DESCRIPTION 

INTRODUCTION 

In the United States two major processes are used in the manufacture of formaldehyde from methanol: the metallic-silver-catalyst combination dehydrogenationoxidation process (silver process), which is used at 35 locations to produce 75% 

of the formaldehyde manufactured, and the metal-oxide-catalyst oxidation process 

(metal oxide process), which is used at 20 locations to produce 25% of the formaldehyde manufactured. The projected annual production growth for each process is 

4 to 5%.1,2 

Two gas-phase reactions are employed to form formaldehyde from methanol: 

Reaction 1 — Dehydrogenation 

CH30H 

(methanol) 

HCHO 

(formaldehyde) 

H2 

(hydrogen) 

Reaction 2 — Oxidation 

CH OH + 

(methanol) (oxygen) 

->- HCHO + 

(formaldehyde) 

H20 

(water) 

The silver process involves the dehydrogenation of methanol (reaction 1) followed 

by oxidation of a portion of the hydrogen evolved to form water, or a combination 

of dehydrogenation and oxidation of methanol (reactions 1 and 2). The metal oxide 

3 

process involves oxidation of methanol by reaction 2. 

The major difference between the two processes is the amount of air mixed with 

the methanol before conversion. Since air and methanol form explosive mixtures 

at concentrations of approximately 6 to 37 vol % of methanol in air, the air/ 

methanol input must be controlled. The metallic-silver-catalyst dehydrogenationoxidation processes maintain an excess of methanol, and methanol concentrations 

are above the explosive range, whereas the metal-oxide-catalyst oxidation processes use an excess of air so that the methanol concentrations are below the lower 

limits of the explosive range. Off-gas from the metallic-silver-catalyst process 

contains 18 to 20% hydrogen and less than 1% oxygen. Off-gas from the metal-oxide-
P.62 

*^a*amm*^nwmw 

III-2 

> catalyst process contains unreacted oxygen and no appreciable concentration of 

hydrogen. 

With the metallic-silver-catalyst process the excess methanol must be separated 

to meet customer specifications. With the metal-oxide-catalyst process the large 

excess of air requires a larger compressor and the process equipment must be larger 

to handle the added air volume. 

METALLIC-SILVER-CATALYST PROCESS 

Process Description 

The process flow diagram shown in Fig. III-l represents a typical continuous metallia 

silver-catalyst process. 

The incoming air (Stream 1) is washed with caustic to remove traces of sulfur 

dioxide, hydrogen sulfide, and other impurities that act as catalyst poisons. ' 

The air is then compressed to 143 kPa and passed through a vaporizer column, where i 

it is heated and saturated with methanol vapor (Stream 2). The heated air and 

methanol vapor must comprise more than 37 vol % methanol in order to be above the 

high explosive limit of the methanol. 

The mixture (Stream 3) then enters a battery of converters. Approximately 80% of 

the methanol feed is reacted for a per-pass conversion ratio of 0.80. The converter 

temperature is maintained at approximately 635°C (ref. 5) by heat generated by 

the oxidation of a portion of the hydrogen evolved and/or by methanol oxidation. 

The hot effluent gases (Stream 4) are quickly cooled to prevent decomposition of the 

formaldehyde formed. Cooling is accomplished by heat interchange with the feed 

mixture in the vaporizer and by then introducing the gas into the primary absorber. 

The primary-absorber liquid is an aqueous solution of formaldehyde and methanol. 

A portion of this liquid is withdrawn from the bottom of the absorber column and 

recirculated to the top. The remainder (Stream 5) is pumped to the product fractionation column. The uncondensed vapors and noncondensable gases (Stream 6) are 

withdrawn from the top of the primary-absorber column and fed to a secondary absorbe 
A <P 

O 

METHAUOI . 

STORAKqlE. 

CAUSTIC WATER 

A :R 

® - STORAGE EMISSION S 

? ) - MMJDUklG, EMlb*>»OUS 

y ) - FUGITIVE EMlS-blOWS -

OVERAL L PUAU T 

® - SECONDAR Y EMI^IOk J POTENT 

I 

PRODUCT 

FRACTIO U ATlOU 

Fig. III-l. Flow Diagram for Uncontrolled Model Plant Producing Formaldehyde from 

Methanol with the Metallic-Silver-Catalyst Process 
P.64 

III-4 

The major portion of the uncondensed vapors is recovered in the secondary-absorbe* 

column through contact with demineralized water, and the off-gas is vented (Vent 

The weak formaldehyde/methanol solution (Stream 7) withdrawn from the bottom of 

the secondary-absorber column is pumped to the primary-absorber column and used 

as makeup solution. 

The methanol-containing formaldehyde solution (Stream 5) is pumped to a fractionation column, where methanol is recovered. This vacuum distillation step yields an 

overhead product of approximately 99% methanol for recycle to the reactor and a 

bottom product of formaldehyde solution containing less than 1% methanol. The 

* 

methanol vapor from the top of the column is condensed and recycled to the vaporiz 

(Stream 9). Uncondensed vapors are vented (Vent B) . The formaldehyde solution 

from the bottom of the fractionation column is pumped to product storage tanks. 

When required by customer specifications the solution is treated for removal of 

trace amounts of formic acid by being passed through an ion exchange system before 

being stored. As a final step, water is added to provide a suitable concentration 

for storage and shipping. Reported yields for the metallic-silver-catalyst proces 

range from 83 to 92%.1' 

All product storage tanks are heated to prevent polymer formation and precipitation in storage. A series of tanks are used to blend and adjust the solution to 

the desired formaldehyde and methanol concentrations before it is shipped to the 

customer. . 

Process Variations 

Vacuum distillation is described for the model-plant process step used for recover 

of the excess methanol in the product stream. However, the uncondensed gases and 

vapors discharged from the vacuum producer must be vented or otherwise dealt with. 

Many plants use pressure distillation equipment operated at increased temperature 

instead of vacuum fractionation, which dispenses with the need for the vent assoc: 

ated with the fractionator vacuum producer (Vent B, Fig. III-l) and therefore 

eliminates the emission source. The quantity of dissolved gases in the feed to 

the distillation column is very small. 

Process development efforts have been directed toward reducing the excess methano 

in order to eliminate the fractionation step. The addition of water to the metha 
P.65 

III-5 

to form a feed mixture containing 30 to 50 vol % water can produce a product containing 7 to 8 wt % methanol, 

some markets. 

This concentration of methanol is suitable for 

Many approaches have been taken by the various plants to improve efficiency for 

heat utilization. In some plants heat from the reactor is used to heat the 

methanol distillation reboiler or to generate steam to drive the fractionationcolumn vacuum pump. 

C. METAL-OXIDE-CATALYST PROCESS 

1. Process Description 

The process flow diagram shown in Fig. III-2 represents a typical continuous metaloxide-catalyst process. The catalyst system most often used is ferric molybdate. 

Incoming air (Stream 1) may be washed with caustic solution in a packed tower to 

remove dust and trace impurities. The air is then compressed, along with the 

recycle gas (Stream 5) to 143 kPa. Recycle of a portion of the oxygen-lean vent 

gases lowers the oxygen content of the air feed stream to below 10.9%. This reduces the explosion hazard of the feed mixture and increases the equipment output 

by reducing the amount of excess air required to keep the methanol concentration 

below the low explosive limit. 

A portion of the air is passed through the vaporizer column, where it is saturated 

with methanol (Stream 2). The methanol-saturated air is then mixed with the remaining air and preheated by heat exchange with the product gas leaving the converter. 

The feed gas mixture (Stream 3) then enters the converter. Conversion ratios of 

97% are obtained. The converter, heated by the exothermic oxidation reaction, is 

maintained at 345°C (ref. 5) by boiling heat transfer fluid in the reactor shell. 

Steam is generated by condensation of the heat-transfer fluid vapors. 

± 

The product gas (Stream 4) is cooled by heat exchange with the feed gas mixture 

and then quenched in the absorber column. The formaldehyde and methanol are removed from the gas stream by absorption in the aqueous solution. The unabsorbed 

gases and vapors exit at the top of the absorber column. A portion (60 to 80%) 

of this gas is recycled (Stream 5) and the remaining gas is vented. The product 
***am*a*m 

©J 

METHAUOL 

STORAGE 

CAUSTIC 

WATER 

li 

A\R 

^ 

MIXE R 

STEAM 

<^^^* ' 

COMPRESSOR VAPORVZER 

®* 

SPewrr 

CAUSTIC 

V/ASM 

(§) - STORAGE EMvSStOhJS 

(£) - HA»JDL»U& EMISSION S 

© - FUGITIVE EM\SSIOV4S - OVERALL PLAWT 

(g) - SECONDARY EMISSlO M POTEKITlAL. 

<J> 

^ 

RECYCLE G»Ai 

" ^ 

STEAM 

COUD. 

f® 

13 

CONVERTER DO/VTWERM 

STORAGE 

STEA ^ 

G,EMERATOR 

~& 

OFF-frA*, .© 

^ 

ReG»EKIERAUT 

^ 

DEMiUERAUZEO 

-,\ WATER 

~ A© 

• 

< * 

FORMALQEMroe 

< £ > SOLUTION 

SPEUT 

SALTS 

PRODUCT IOW 

ABSORBER EVCMAkl^ER 

PRODUC T 

STORAGE 

Fig . III-2 . Flow Diagram fo r Uncontrolled Model Plant Producing Formaldehyde from 

Methanol with the Metal-Oxide-Catalyst Process 
1. 

III-7 

solution drawn from the bottom of the absorber column contains approximately 0.8% 

methanol and 0.005% formic acid. The solution is usually treated in an ion exchange 

system to reduce the acidity and is then stored. As a final step water is added 

to provide a suitable concentration for storage and shipping. Process yields of 

91 to 93% are reported for the metal-oxide-catalyst process. ' 

The formaldehyde yield from the metal-oxide-catalyst process is higher than that 

from the metallic-silver-catalyst process and the metal-oxide-catalyst process is 

simpler, because methanol distillation is not required. The equipment costs for 

the metal-oxide-catalyst process are greater because of the large volume gas 

streams,- also, because of a lower concentration of formaldehyde in the product 

gas stream, the absorber column diameter is larger and the operating temperature 

is lower than those used with the metallic-silver-catalyst process. 

Process Variations 

The industry makes use of various catalyst compositions and methods and extent of 

heat recovery. Otherwise, the processes used are basically similar. Many older 

plants do not recycle a portion of the absorber-column vent gas. For these plants 

the vent gas volume and the ratio of volatile organic compounds emitted per unit 

of product produced are increased. 

The oxide catalyst is not susceptible to poisoning by traces of sulfides in the 

air feed; thus many plants filter the incoming air rather than utilizing caustic 

scrubbers. 

OTHER PROCESSES 

Formaldehyde by Partial Oxidation of Methane 

Considerable research has been devoted to production of formaldehyde directly 

from methane. The process is more complex and requires a higher capital investment than do processes utilizing methanol. Commercial attempts to produce formaldehyde from natural gas or methane has had limited success and the process currently is not used in the United States. 

Z9'd 
IV-1 

IV. EMISSIONS 

Emissions in this report are usually identified in terms of volatile organic compounds (VOC). VOC are currently considered by the EPA to be those of a large 

group of organic chemicals, most of which, when emitted to the atmosphere, participate in photochemical reactions producing ozone. A relatively small number of 

organic chemicals have low or negligible photochemical reactivity. However, many 

of these organic chemicals are of concern and may be subject to regulation by EPA 

under Section 111 or 112 of the Clean Air Act since there are associated health 

or welfare impacts other than those related to ozone formation. 

The process emissions estimated for the formaldehyde model plants are based on 

the emissions reported in responses to EPA's requests for information from selected 

companies, on EPA emission testing data, and on data obtained during visits to 

Ceianese and Borden formaldehyde production plants (see Appendix E). Also used 

in sizing and design of the model plants were data from the EPA studies, SRI 

reports,: formaldehyde data compiled by J. F. Walker, and an understanding of 

the process chemistry and yields. 

A. FORMALDEHYDE FROM METHANOL PROCESS USING A METALLIC SILVER CATALYST 

l

- Model Plant 

The model plant* for this study has a capacity of 45 Gg/yr, based on 8760 hr of 

operation per year.** Although not an actual operating plant, it is typical of 

many plants built recently. The plant utilizes the model metallic-silver-catalyst 

process (Fig. III-l) and best fits today's formaldehyde manufacturing and engineering technology for that process. 

Typical raw-material, intermediate, and product-storage tank capacities were estimated for the 45-Gg/yr model plant. Storage tank requirements are given in 

Sect. IV.A.2.e. Estimates of potential fugitive sources, based on data from existing 

*See p. 1-2 for a discussion of model plants. 

*Process downtime is normally expected to range from 5 to 15%. If the hourly 

rate remains constant, the annual production and annual VOC emissions will be 

correspondingly reduced. Control devices will usually operate on the same cycle 

as the process. From the standpoint of cost-effectiveness calculations, the 

error introduced by assuming continuous operation is negligible. 
IV-2 

plants, are given in Sect. IV.A.2.d. "" Characteristics of the model plant that 

are important in air-dispersion modeling are shown in Appendix B. 

Sources and Emissions 

Uncontrolled emission rates and sources for the metallic-silver-catalyst process 

are summarized in Table IV-1 and are described below. The process emission rates 

are based on emission data from existing plants. Potential storage, handling, 

fugitive, and secondary emissions were calculated from characteristics of the 

plant and from data on existing plants (see Table IV-2). 

Absorber Vent — The absorber vent (Vent A, Fig. III-l) is the principal source 

of emissions from the formaldehyde production plant. The volatile organic compounds (VOC) in the vent gas include unreacted methanol, formaldehyde, methyl 

formate, and methylal (see Table IV-3). Also included in the vent gas are hydrogen, 

methane, carbon monoxide, carbon dioxide, nitrogen, water vapor, and a small amount 

of unreacted oxygen. The composition of the absorber vent varies somewhat with 

the catalyst's age and < 

is given in Table IV-1. 

4 

the catalyst's age and activity. The average emission during normal operation 

Product Fractionator Vent — A product fractionator operated under vacuum is used 

to separate and recover unreacted methanol from the product stream. A steam ejector 

or vacuum pump is employed to produce the vacuum required. Emissions from this 

source (Vent B) include methanol vapor, formaldehyde, water vapor, and a small 

amount of inert gases (see Table IV-3). 

Intermittent Air Emissions — The formaldehyde plant is normally operated at design 

conditions to achieve highest yields. It is shut down when product inventories 

are filled. Since the metallic-silver-catalyst process operates above the upper 

explosive limit of methanol, the plant startup procedure must be handled carefully. 

Unstable conditions are often encountered and explosions can occur in the methanol 

vaporizer and the reactor. Various startup procedures are used in the industry. 

Usually during startup the output from the reactor is vented until stable operation 

is achieved and an acceptable yield ratio is obtained. The flow is then switched 

' 2 

into the absorber. The total startup time is 1 to 2 hr. The reactor feed rate 

varies as the startup proceeds. Initially the reactor produces mainly carbon 
P.70 

IV-3 

Table IV-1. Total VOC from Uncontrolled Emissions Produced by 

Formaldehyde Metallic-Silver-Catalyst Process in a Model Plant 

Emission Source 

Stream 

Designation 

(Fig.III-l) 

Emissions 

Absorber 

Product fractionato r 

b 

Intermittent 

Hethanol storag e 

Formaldehyde storag e 

Handling 

Fugitive 

Secondary 

Total 

A 

B 

C 

D 

D 

F 

H 

K 

Ratioa 

(g/kgj 

4.73 

1.56 

0.11 

0.08 

0.03 

0.01 

1.08 

0.01 

Rate 

(ka/hr) 

24.5 

8.2 

0.28 

0.43 

0 . 2 

0 . 1 

5.7 . 

0.03 

7.63 39.44 

9 of total VOC per kg of 37% formaldehyde solution produced. 

b 

Average rat e for entir e year, based on 8 startup s per year and flow of one-half th e 

normal rat e during startup . 

Table IV-2. Model Plant Storage 

1 

1 

_^ontent 

Ethanol (feed) 

formaldehyde 

Methanol (recycle) 

Methanol (feed) 

p

°rmaldehyde 

Tank Size No. of Tanks Turnovers 

(m^) Required Per Year 

Metallic-Silver-Catalyst Process 

190 2 68 

190 4 45 

4 . 1 * 

Metal-Oxide-Catalyst Process 

190 2 65 

190 4 45 

Bulk Liquid 

Temperature 

~(°C) 

25 

54 

38 

25 

54 

s

urge tank. 

I 
P.71 

IV-4 

Table IV-3. Emission Composition for 

Model Metallic-Silver-Catalyst Process6 

Component 

VOC 

Formaldehyde 

Methanol 

Methyl formate , 

Methylal , 

Combustible gases ' 

Hydrogen 

Methane 

Carbon monoxide 

Other gases 

Oxygen 

Nitrogen 

Carbon dioxide 

Water vapor 

Total 

Absorber 

Composition 

(wt %) 

0.75 

(0.06) 

(0.14) 

(0.36) 

(0.19) 

2.38 

(1.69) 

(0.28) 

(0.41) 

93.96 

(0.42) 

(86.64) 

(6.90) 

2.91 

100.00 

Vent 

Ratio 

(g/kg) 

4.73 

(0.36) 

(0.89) 

(2.27) 

(1.20) 

14.97 

(10.59) 

(1.77) 

(2.61) 

590.23 

(2.63) 

(544.23) 

(43.37) 

18.25 

628.17 

Emissions 

Fractionator 

Composition . 

(wt %) 

83.16 

(17.49) 

(65.67) 

0.94 

15.90 

100.00 

Vent 

o 4.- b Ratio 

(g/kg). 

1.58 

(0.33) 

(1.24) 

0.02 

0.3013 

1.90 

Emission rates are based on emission data from existing plants; see Appendix E. 

g of emission per kg of 37 wt % formaldehyde solution produced. 
P.72 

IV-5 

dioxide and water vapor. As the temperature rises, the formaldehyde yield increases, thereby enlarging the amount of VOC in the gas vented. The average annual 

emission calculated from this source (see Table IV-1) is based on an average of 

eight startups per year and a flow of one-half the normal rate during startup. 

d. Fugitive Emissions -- Process pumps, valves, and circulating process cooling water 

are potential sources of fugitive emissions. The model plant is estimated to 

1--3 

have 13 pumps, 214 process valves, and 6 relief valves handling VOC. An estimated 6.5 liters of cooling water per kg of product produced is circulated through 

the cooling tower. Fugitive emission factors from Appendix C were applied to 

determine the fugitive emissions shown in Table IV-1. 

e. Storage and Handling Emissions — Emissions result from the storage and handling 

of methanol and formaldehyde. Sources for the model plant are shown in Fig. III-l 

(Source D). Storage tank conditions for the model plant are given in Table IV-2. 

The emissions in Table IV-1 are based on fixed-roof tanks, half full, and a diurnal 

temperature variation of 11.1°C and were calculated based on the emission equations 

from AP-42. However, calculated breathing losses were divided by 4 to account 

for recent evidence indicating that the AP-42 breathing loss equation overpredicts 

. . 6 emissions. 

Since uninhibited formaldehyde polymerizes at a low temperature, concentrated 

solutions (over 30% HCHO) must be kept warm. Therefore the model-plant formaldehyde storage tanks are maintained at above 54°C. Since these tanks are temperature controlled, breathing losses are negligible and emissions given are based on 

working losses only. 

Emissions from the loading of formaldehyde solution into trucks and tank cars 

were calculated with the equations from AP-42, with submerged-fill-pipe loading 

assumed to be used. These emissions are also included in Table IV-1. 

Secondary Emissions -- Secondary VOC emissions can result from the handling and 

disposal of process-waste liquid streams. The potential sources (Source K) that 

exist for the model plant are ion exchange system regeneration and blowdown water 

from the cooling and air-wash towers. The calculated total secondary VOC emission from these sources is given in Table IV-1. Calculations are based on waste-
IV-6 

water data reported by industry and the assumptions that the ion exchange system 

is operated for 10% of the production e 

wastewater evaporates before treatment. 

is operated for 10% of the production and that 5% of the VOC contained in the ' 

B. FORMALDEHYDE FROM METHANOL PROCESS USING A METAL OXIDE CATALYST 

1. Model Plant 

The model plant for this study is based on the metal-oxide-catalyst process 

utilizing vent gas recycling (Fig. III-2). This model process best fits today's 

formaldehyde manufacturing and engineering technology for utilizing a metal oxide 

catalyst. The model plant has a capacity of 45 Gg/yr based on 8760 hr of operation 

per year. 

Typical raw-material and product-storage tank capacities were estimated for the 

45-Gg/yr model plant. Storage tank requirements are given in Sect. IV.B.2.e. 

Estimates of potential fugitive sources, based on data from existing plants, are 

given in Sect. IV.B.2.d. Characteristics of t* 

in air-dispersion modeling are given in Appendix B. 

given in Sect. IV.B.2.d. Characteristics of the model plant that are important 

Sources and Emissions 

Uncontrolled emission rates and sources for the metal-oxide-catalyst process are 

summarized in Table IV-4 and are discussed below. Process emission rates are 

based on emission data from existing plants. Potential storage, handling, fugitive, 

and secondary emissions were calculated from model-plant characteristics and data 

from existing plants. 

Since the process operates below the explosive limit with an excess of air, 

unstable conditions during startup are easily prevented. Venting of the reactor 

during startup is not required. 

Absorber Vent -- The product absorber vent (Vent A, Fig. III-2) is the main source 

of emissions from the formaldehyde production plant. The VOC components in the 

vent gas include methanol, formaldehyde, and dimethyl ether (Table IV-5). Also 

included in the vent gas are carbon monoxide, carbon dioxide, nitrogen, oxygen, 

and water vapor. 
P.74 

>n 

IV-7 

Table IV-4. Total VOC Uncontrolled Emissions for Formaldehyde 

Produced by Metal-Oxide-Catalyst Process in a Model Plant 

Stream 

Designation 

Source (Fig.III-l) 

Absorber 

Methanol storage 

Formaldehyde storage 

Handling 

Fugitive 

Secondary 

Total 

A 

D 

D 

F 

H 

K 

Ratio 

(g/kg) a 

3.15 

0.08 

0.03 

. 0.01 

0.74 

0.05 

Emissions 

Rate 

(kg/hr) 

16.3 

0.44 

0.2 

0.1 

3.7 

0.2 

4.06 20.7 

g of total VOC per kg of 37% formaldehyde solution produced. 
P.75 

IV-8 

Table IV-5. Absorber Vent Gas Composition for 

Model Metal-Oxide-Catalyst Process3 

Emissions 

Component 

Composition 

(wt %) 

0.27 

(0.04) 

(0.16) 

(0.07) 

95.45 

(7.91) 

(86.09) 

(0.19) 

(1.26) 

4.28 

100.00 

Ratio 

(q/kq) 

3.15 

(0.44) 

(1.93) 

(0.79) 

1124.39 

(93.20) 

(1014.02) 

(2.28) 

(14.89) 

50.37) 

1177.91 

VOC 

Formaldehyde 

Methanol 

Dimethyl ether 

Other gases 

Oxygen 

Nitrogen 

Carbon dioxide 

Carbon monoxide 

Water vapor 

Emission rates are based on emission data from existing plants; 

see Appendix E. 

3g of emission per kg of 37 wt % formaldehyde solution produced. 

•an 
P.76 

IV-9 

The emission composition and flow rates are especially affected by the percent of 

absorber gas recycled. By recycling a portion of the oxygen-lean vent gas, the 

oxygen concentration in the reactor feed mixture can be reduced, making it possible 

for the concentration of methanol to be increased without an explosive mixture 

being formed. This reduces the volume of reaction gases and thus reduces equipment size and horsepower required to drive the compressor. Recycling reduces the 

9 

emission rate and enhances the reactor equilibrium to produce a higher yield. 

The effect of recycling on absorber vent emissions can be seen by the comparison 

of absorber vent gas composition for recycling and nonrecycling operations given 

in Table IV-6. 

Other variables that affect the absorber vent emissions are catalyst formulation, 

catalyst age, absorber temperature, and strength of formaldehyde produced. The 

catalyst formulation can affect the overall process yield and thus the amount and 

type of by-products or emissions produced. Also, product yields tend to decrease 

as the catalyst ages. Lowering the absorber temperature increases its efficiency 

and thus lowers the VOC emissions from the absorber. As the strength of the formaldehyde produced increases, the partial pressure due to the formaldehyde increases, 

thus increasing the relative amount of formaldehyde in the vent emission. 

The model-plant average absorber vent emission during normal operation is given 

in Table IV-4. A recycle rate of 63 vol % for the product absorber vent gas was 

calculated based on emissions data. 

Fugitive Emissions — Process pumps and valves are potential sources of fugitive 

emissions. The model plant is estimated to have 8 pumps, 176 process valves, and 

4 relief valves handling VOC. An estimated 6.5 liters of cooling water per kg of 

product produced is circulated through the cooling tower. Fugitive emission factors 

from Appendix C were applied to determine the fugitive emissions shown in Table IV-4. 

Storage and Handling Emissions — Emissions result from the storage and handling 

of methanol and formaldehyde. Sources for the model plant are shown in Fig. III-2 

(Source D) . Storage tank conditions for the model plant are given in Table IV-2. 

The emissions in Table IV-4 are based on fixed-roof tanks, half full, and a diurnal 

temperature variation of 11.1°C and were calculated based on the emission equations • 
P.77 

IV-10 

Table IV-6. Absorber Vent Emission Ratios for Recycled Vent Gas vs 

Nonrecycled Vent Gas for Model Metal-Oxide-Catalyst Process 

J^rrossiqn Ratio (gAg) 

Recycled Nonrecycled 

Component Vent Gas Vent Gas 

Total VOC 3.2 12.7 

OtherC 1174.8 5440.0 

Total 1178.0 5452.7 

ag of total VOC per kg of 37% formaldehyde solution produced. 

Includes formaldehyde, methanol, and dimethyl ether. 

c • • 

Includes nitrogen, oxygen, carbon dioxide, carbon monoxide, and water. 

• ^ , 
P.78 

IV-11 

from AP-42. However, the breathing losses were divided by 4 to account for recent 

evidence indicating that the AP-42 breathing-loss equation overpredicts emissions. 

d. 

Since uninhibited formaldehyde polymerizes at low temperature, concentrated solu7 

tions (over 30% HCHO) must be kept warm. Consequently the model-plant formaldehyde storage tanks are maintained above 54°C. Breathing losses are negligible 

because the tank temperature is controlled. Emissions therefore are based on 

only working losses. 

Emissions from the loading of formaldehyde solution into trucks and tank cars 

were calculated with the equations from AP-42. These emissions are included in 

Table IV-4. 

Secondary Emissions -- Secondary VOC emissions can result from the handling and 

disposal of process-waste liquid streams. The potential sources (Source K) that 

exist for the model-plant are ion exchange system regeneration, blowdown water 

from the cooling and air-wash towers, and emissions from the heat-transfer fluid 

system vent. The total secondary VOC emission from these sources is given in 

Table IV-4. Emissions were calculated based on wastewater data reported by industry 

and the assumptions that the ion exchange system is operated for 100% of the production and that 5% of the VOC contained in the wastewater evaporates before treatment. 
Introduction to 

Industrial Chemistry 

HOWARD L. WHITE 

CIBA-GEIGY Corporation (Ret.) 

A Wiley-lnterscience Publication 

JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • Singapore 
P.80 

jr^&m 

who: 

and v 

(w 

an 

Copyright © 1986 by John Wiley & Sons, Inc. 

All rights reserved. Published simultaneously in Canada. 

Reproduction or translation of any part of this work 

beyond that permitted by Section 107 or 108 of the 

1976 United States Copyright Act without the permission 

of the copyright owner is unlawful. Requests for 

permission or further information should be addressed to 

the Permissions Department, John Wiley & Sons, Inc. 

Library of Congress Cataloging in Publication Data: 

White, Howard L., 1922-

Introduction to industrial chemistry. 

"A Wiley-lnterscience publication." 

Includes bibliographies and index. 

1. Chemistry, Technical. I. Title. 

TP145.W46 1986 

ISBN 0-471-82657-X 

660.2 86-5643 

Printed in the United States of America 

10 9 8 7'6 5 4 3 2 1 
106 ORGANIC CHEMICAL PROCESSES 

Another source of malcic ;inhydridc is the mother liquors of the phthalic 

anhydride process using the naphthalene process. 

4.8 INDUSTRIAL CHEMICALS FROM METHANE 

Wc have now discussed six of the seven chemical substances derived from 

petroleum From these petrochemicals are derived 90% of all commercially 

prepared organic substances. The seventh is methane, which wc have encountered four times before in this hook: First, there was the synthesis of ammonia 

from nitrogen and hydrogen. Ihe latter derived from methane and steam by the 

reaction forming synthesis gas. a carrion monoxide-hydrogen mixture (see Section 2.3.1.A). Second, we discussed the significant quantity of methane available from anaerobic digestion of sewage sludge (see Section 3.2.4.B). Third, 

wc discussed the hydroformylation reaction, addition of methane-derived synthesis gas to olefins to yield aldehyde mixtures (sec Section 4.3.3). Fourth, the 

preparation of mclhanol from syngas was discussed in detail in Section 4.2.5. 

Wc now discuss various large-scale products that use methanol in their manufacture. The approach is that of Frank (I982). who discussed these products 

under two headings: (I) traditional uses of mclhanol. and (2) new and evolving 

uses of methanol. Wc first briefly review the traditional uses: 

4.8.1 Traditional Uses of Methanol 

A. Formaldehyde 

The manufacture of fonnaldchydc is carried oui by removal of hydrogen from 

methanol by a catalytic process. This process was referred lo in the discussion 

of ethylene glycol in Section 4.2.9.A. The most up-to-date process involves the 

use of silver needles or gau/cs at 600T . The methanol is exposed for about ,t' 

0.01 second, and very little mclhanol is left. Air is added lo Ihe mixture to^ y 

combine with the hydrogen. This liberates heal, which is needed for the cndolhermicVlchydrogciialion slcpj 

This silver catalysis reaction resembles the ethylene oxide synthesis in that 

the metal significantly reacts only whcn.il is covered with a layer of oxygen. 

The mechanism is shown in these two equations: 

Aq 

CHjOH,,, . 0,adM • CH,0(ad51 + OH,,*, 

fiOO-C 

CH3OIMS| • CHpOu,, t H(adS| 

For a further review of this topic, sec Rylandcr (1983. pp. 19-20). 

(jijU^ 

107 4.8 INDUSTRIAL CHEMICALS FROM METHANE 

B. Dimethyl Terephthalate (DMT) 

Polyester liber is made from the raw materials dimethyl terephthalate 

and ethylene glycol 

nCH3OOC-C6H4 -COOCH3 + r»HOCH,CH2OH 

I 

-OOC-C 6 H 4 -COOCH ? C H 2 - + 2nCH3OH 

The process uses p-xylene as a raw material and is a catalyzed air oxidation. 

The most recent approach is to carry out the oxidation to the acid and esterification in one reactor. The oxidation proceeds in two steps. The conversion of 

Ihe second methyl group is difficult, but made easier by the esterification of the 

carboxyl group in p-toluic acid. In this continuous process />-xylene and partly 

oxidized product are introduced at Ihe top ofthe column, and air and methanol 

at the bottom. The catalyst is a Cu-Mn sail of an organic acid, the temperature 

is I00-200°C, the pressure is 5-20 bar. and the residence time is 22 hours. 

CH, CH, 

CH, 

CH,OH 

COOCH, 

COOCH, COOCH, 

The use of dimethyl terephthalate in this process is gradually being displaced 

by use of terephthalic acid. Further background on this process is given in 

Weissemel and Arpe (1978. pp. 341-44). 

C. Methylamlnes 

Melhylamincs are prepared from methanol and ammonia at 250-500°C. A laboratory-trained chemist would not be able to predict that this reaction would 

pmcced to a good yield using these raw materials. Methyl chloride would be 

chosen. However, by using Ihe appropriate catalyst (e.g., aluminum silicate at 

10-200 bar), very high selectivity is obtained. 

CH3OH + NH3 - CHjNH;, + HjO 

The mono- and dialkylation products arc favored by excess ammonia and by 

addition of trimcthylaininc. The workup consists of a pressure and an extractive 

distillation. For the latter technique, see Section 9.1.1 and Weissermel and Arpe. 

(1978. p. 45). 
P.82 

ST-AF - 00?39/>>/o 

1969 c.3^ ' '** 

19o 9 DIRECTORY OF 

CHEMICAL PRODUCERS 

UNITED STATES OF AMERICA 

Information in this Directory it for tho solo 

and prtvata usa of sponsors of tho 

^\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 OT wnomicM rrooucars rnjsjwm* 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK, NC 
P.83 

333 RAVENSWOOO AVENUE 

MENLO PARK, CALIFORNIA 94025 

(415) 859-3627 

FAX: (415)326-5512 

TWX: 910-373-2046 

TELEX: 334466 

S.^S^ir**""-

 Un**WttM - " "•»*— — -*.«-«. ea^ma, , 

.*«**»»*, 
P.84 

>RODUCTS , 

1989 DIRECTORY OF CHEMICAL 

UNITED STATES 

ormaldehyde (Formic aldehyde) (Methanal) (Methyl aldehyde) 

Methylene oxide) (Oxomethane) (Oxymethylene) , 

fcrden Inc. IOI^ . 

Borden Chemical Division 

Adhesives and Chemicals Division 

Perkins Industries, subsidiary 

3orden Chemicals and Plastics 

Partnership 

Demopolis. Alabama ^G 

Diboll. Texas 31 

Fayetteville. North Carolina ~UX> 

Fremont, California 104-

Kent. Washington V\ 

La Grande. Oregon 3 2 

Louisville, Kentucky V 

Missoula, Montana 4( 

Sheboygan, Wisconsin &t 

Springfield. Oregon M>1 

Vicksburg, Mississippi 2-1 

Geismar, Louisiana 236 

^w9 

f 

PRODUCERS 

Pf* *4-

Annual Capacity 

(Millions of Pounds) 

-ft* re 

BTL Specialty Resins Corp. 

Chembond Corporation 

Hampton, South Carolina 23 

Houston, Texas so 

Malvern, Arkansas 5Q 

RndaIusia, Alabama 32 

Moncure, North Carolina 5^ 

Springfield, Oregon 63 

. Winnfield, Louisiana' 32 

P-P2-

P-Pl 

P-P I 

P-fS. 

P-P2, 

0. B. Western 

New Mexico Adhesives 

g.l. du Pont de Nemours 81 Company, 

Inc. 

Chemicals and Pigments 

Department 

Virginia, Minnesota 

Las Vegas, New Mexico * 3 P-p 1 \r4fus**-

Belle, West Virginia 

GWMOIIII Now Jorooy 

2iT 

Healing Springs, North 102. 

Carolina 

La Porte, Texas '45 

Parkersburg, West Virginia i?l 

Toledo, Ohio ii£ 

0VF Corporation 

GAF Chemicals, subsidiary 

Georgia-Pacific Corporation 

Chemical Division 

Calvert City, Kentucky 

Texas Citv. Texas 

Hercules Incorporated 

Operations Division 

Hoechst Ceianese Corp. 

Engineering Plastics Group 

Hoechst Ceianese Chemical Group, 

Inc. 

Albany, Oreqon 7J 

Columbus, Ohio IS 

Conway, North Carolina <& 

Crossett, Arkansas —7 5 

Lufkm, Texas K$ 

Russellville. South Carolina ^ t 

Taylorsville, Mississippi 22 vio""a

 fipnroir *ro, , 

Louisiana, Missouri i l 

?-fl 

P-PS. 

F-PA 

P-R2 

Bishop, Texas ?*S 

"Jiirnational Minerals & Chemical 

Corporation 

?itman-Moore, Inc., subsidiary 

Industrial Chemicals Division 

Newark, New Jersey 54 

Rock Hill. South Carolina?* 

^:nsanto Company 

Monsanto Chemical Company 

PVP~CorpT 

Seiple. Pennsylvania 61 

Chocolate Bayou, Texas O . 

Springfield. Massachusetts * M 

bright Chemical Corporation 

•pey.iSS£-

11^8 Citv. 6reaon t 

Acme, North Carolina 

~T\\£4<i&*~e. , AlA, 

SI 

»1 

P-Pi 

P-P2. 

P-PI 

P-?( 

P-Pi 

P-PI 

P-pl 

P-Pi 

TOTAL 

Jit. 

1& 

500 

225 

320 

400 

275 

100 

100 

160 

165 

105 

165 

105 

218 

160 

-125. 

176F>lgO 

•IOOO) 1920 

120 

120 

135 

Note: Capacities are on a 37% basis. 

Source: SRI International estimates as of January 1, 1989. ~fo>J 43o7 T4v; 

Formaldehyde-sodium bisulfite adduct (See: Sodium 

formaldehyde bisulfite) 

Formamidine disulfide dihydrochloride 

Frank Enterprises, Inc. Columbus, Ohio 

SRI International 871 
P.85 

&A«*»Ut*l Pvulctct* BptoptU 

Subscription for: 

Radian Corporation 

TtteuutdUdltt Chemical Products 

Box 232 • Cortland, New York 13045 • (607)753-8700 
P.86 

(ZAtmiCAl "PXKUCUCU SuKfeftll* ^ A Reporting Service of 

r • ~ THenatvttUCHEMICAL PRODUCTS 

JUNE 1983 Cortland, New York 13045-0232 

Previous Report- December 1981 FORMALDEHYDE 

FOCUS Production of formaldehyde in 1982 amounted to 4.69 billion pounds (37% basis) according to preliminary 

data from the U.S. International Trade Commission. This represents a decline of 18% from die S.72 billion pounds produced 

in 1981 and is 26% below the most recent high of 6.38 billion pounds turned out in 1978. The record for formaldehyde 

output was set in 1973 when 6.4 billion pounds was produced. 

The decline in formaldehyde output over the past several yearsjs due principally tothe sharp fall off injew housing 

construction and domestic aul6Tnobde^roducfi61TfF6rirtfieif most recent Tflghs reached in 1978. New housing starts In 1982 

T6TalIedT":06 million units, down 47%Tr6m" the"2.03 mfllTon"units started inl?78 while domestic automobile production fell 

by 45% between 1978 and 1982. The largest uses for formaldehyde, accounting for slightly less than 3/5 of demand, are in 

the manufacture of urea (UF), phenol (PF) and melamine (MF) formaldehyde resins which are heavily dependent on transportation and construction applications. Building and construction, and related end uses, account for 75-80% of UF resin 

consumption and 70% or more of PF resin demand while MF resins are about 50% dependent on construction outlets. 

UF and PF resins are widely used as bonding adhesives in the production of softwood plywood, hardwood plywood, 

particleboard and fiberglass insulation. Other construction related applications are in decorative laminates and electrical moid* 

ings. Production of particleboard, the largest outlet for UF resins, fell by 19% in 1982 and was 36% below the cyclical peak 

reached in 1978. Hardwood plywood production declined by 11% in 1982 and was 41% below that of 1978. Softwood plywood production declined by 6% in 1982 and was down by 25% from the peak reached in 1978. The decline in automobile 

production also impacted on consumption of PF resins used in friction materials; foundry and shell moldings; and coated and 

bonded abrasives. 

Although the Consumer Products Safety Commission (CPSC) banned the use of urea formaldehyde foam in 1982 as 

an insulation material for homes and schools, the ban had little immediate impact on formadehyde demand since the adverse 

publicity and threat of a ban had all but eliminated the use of UF foams as an insulation material since this application peaked 

in 1977/1978. 

OUTLOOK With new housing starts up substantially in the first half of the year to an annual rate of 1.6-1.7 million 

units, formaldehyde output should increase by 12-15% in 1983 compared to the depressed level of output in 1982. In the 

first five months of 1983, formaldehyde production amounted to 2.25 billion pounds, or at an annual rate of 5.4 billion 

pounds. In addition to housing starts, automobile production was up by 25% in the first half of the year. 

With interest rates, particularly for mortgages, again approaching 14%, it is unlikely that the current pace of new 

housing starts can be sustained for the balance of the year. Overall starts will probably end the year at 1.5-1.6 million units -

still a significant increase compared to 1982. Demand for domestically produced new cars will also slacken in the second half 

if interest rates remain at the higher levels for the rest of the year. 

As in the past, the outiook for formaldehyde is dependent on prospects for automobile and housing. Although there is 

somewhat of a backlog of pent up demand for housing based on population growth and demographics, the prospect of new 

housing starts reaching the 2 million unit per year level in the face of expected high real interest rates over the next several 

years is unlikely. Automobiles, however, wear out with the average age of cars on the road currently over 7 years, up from 5 

years in 1978. The backlog of demand for new cars will probably keep automobile production up for several years compared to 

the low levels reached at the start of the decade. It will probably take several years for formaldehyde production to exceed the 

6 billion pound level reached in 1973 and 1978 when new housing starts were over 2 million units. 

The debate over formaldehyde emissions from pressed wood products is not expected to be resolved for several more 

years due to the complexity of the problem compared to the UF foam case. The recent judicial setback against the CPSC ban 

on urea formaldehyde foam insulation will not, however, revive the end use. Wood industry efforts in die meantime to minimize or lessen fugitive emissions from pressed wood products, particularly particleboard, should diminish the threat of a 

ban against these products for a long time. 

PRICING The current list price for 37% uninhibited formaldehyde is 8.8 cents per pound with actual selling prices 

discounted. Any significant increase in demand and/or stronger selling prices for methanol, die feedstock from which formaldehyde is made, could give rise to increases in actual and list prices. 

AVERAGE PRICES RANGE - FORMALDEHYDE - 37% 

CENTS PER POUND - UNINHIBITED - DELIVERED - GULF 

1960 1965 1970 1975 1979 1980 1981 1982 1983 1984 1985 1987 

Trade List 4.3 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 

Average Sales 3 3 2 3 7 7 8 

SUPPLY AND DEMAND Millions of Pounds...37% Basis Estimated Domestic U.S. 

1960 1965 1970 1975 1979 1980 1981 1982 1983 1984 1985 1987 

Capacity 2450 3480 5315 8385 8875 8750 8950 8695 8695 

Production 1872 3107 4427 4558 5971 5555 5720 4691 

Exports 12 10 17 127 20 16 11 10 

Demand 1860 3097 4410 4431 5951 5539 5709 4681 5400 5700 5900 6300 

AVAILABILITY There are currently thirteen producers of formaldehyde with about 50 producing units^In recent 

years the bulk of output (68-69%) was consumed captively for the production of resins and other derivatrvesTDuring 1982 

many formadehyde plants were shut down for varying periods of time. Such plants, particularly those closely tied to facilities 

making resin for plywood and particleboard, are relatively small, and shut down and start up costs little. Capacity overall is 

more than adequate to satisfy captive and merchant market demand. Additional rationalization is expected with reduction of 

capacity over the next several years. 
Hercules 

IMC 

Monsanto 

Nuodex 

Rekhhold 

Wright 

170 

135 

690 

130 

590 

80 

PRODUCERS AND CAPACITIES - FORMALDEHYDE - 37% BASIS - MM LBS 

PRODUCER 1983 CAPACITY PRODUCER 1983 CAPACITY 

Borden 1575 

Ceianese 2040 

Du Pont 1470 

GAF 250 

Georgia-Pacific 1095 

Getty-Chembond 410 

Gulf Oil 60 

TOTAL 8695 

Based on announced capacities and trade estimates without allowing for unannounced shutdowns. At the end of 1982 

Reichhold sold it Moncure, N.C. plant, with a rated capacity of 120 million pounds, to the Chembond Division of 

Getty Oil. Also in 1982, Tenneco sold its Fords, NJ. plant with a rated capacity of 130 million pounds to Nuodex, 

and the Garfield, N.J. plant, rated at 55 million pounds, to Kalama Chemical along with other facilities at those 

locations. Nuodex is operating the Fords plant but the Garfield formaldehyde unit has not been operating. In late 

1981, Occidental (formerly Hooker) shut down a 135 million pound per year formaldehyde plant. 

END USES The largest end use for formaldehyde, accounting for slighdy less than 1/3 of consumption in 1982, is in 

the manufacture of urea formaldehyde resins. UF resins are used primarily as bonding adhesives for pressed wood products 

such as plywood and particleboard, with particleboard applications dominating, taking about 75-80% of UF resin output and 

plywood 8-10%. Other uses for UF resins are in protective coatings. Phenol formaldehyde (PF) resins are the second largest 

use, accounting for about 1/5 of formaldehyde consumption. The largest uses for PF resins are as adhesives for plywood, 

particleboard and fiberglass insulation, which account for about 2/3 of consumption. Other uses for PF resins are in molding 

compounds, laminating, friction materials, abrasives and coatings. Melamine formaldehyde (MF) resins, a relatively small 

outlet, are used in molding compounds, decorative laminates, dinnerware, coatings, paper and textile treatments. 

Reaction of formaldehyde with acetaldehyde gives pentaerythritoi which is used to make alkyd resins, explosives, 

synthetic lubricants, and multifunctional monomers. Formaldehyde is polymerized to give polyacetal resins which are molded 

into engineering plastic parts for appliances, consumer products, plumbing and hardware, and industrial and automotive 

products. Reaction of formaldehyde with acetylene gives 1,4-butyne diol which is hydrogenated to 1,4 butane diol, (1,4-BD). 

1,4-BD is used to make polybutylene terephthalate plastics but its major use is in the manufacture of tetrahydrofuran (THF). 

Polyvinyl pyrrolidone is also made from from 1,4-BD via the intermediate butyrolactone. Reaction of formaldehyde with 

ammonia yields hexamethylenetetramine which is used primarily to cure phenolic molding compounds. It also has use in the 

manufacture of chelating agents, explosives, and bactericides. 

END USE PATTERN - 1982 ESTIMATE 

DERIVATIVE PERCENT 

Urea Formaldehyde Resins 31 

Phenol Formaldehyde Resins 22 

Melamine Formaldehyde Resins 4 

Pentaerythritoi 9 

1,4-Butane Diol 9 

Acetal Resins 8 

Hexamethylenetetramine 6 

Methyl Diphenyl Diisocyanates 2 

Miscellaneous 9 

MANUFACTURING Formaldehyde is made from methanol by two processes; the silver catalyzed process where 

formaldehyde is made by a combination dehydrogenation-oxklation process and the metal oxide process where methanol 

is oxidized directly to formaldehyde. In the silver catalyzed process, vaporized methanol, together with air and steam preheated to 100° C, is passed over a thin bed of silver-crystal catalyst. Formaldehyde is formed by dehydrogenation of methanol. 

The reaction is endothermic and requires heat which is provided by burning tiie hydrogen produced in the dehydrogenation 

reaction. The exit gases are quenched and condensed to produce a methanol-formaldehyde solution. The methanolic formalin 

from the absorber can be the final product or else it is distilled to lower methanol content to 1% or less. 

The metal oxide process involves the oxidation of methanol over a catalyst of molybdenum and iron oxide. The 

reactor consists of a multiple tube unit filled with catalyst and having a heat transfer fluid around the tubes. A mixture of 

air and methanol are vaporized and passed into the tubes. Temperatures are on die order of 300° C. The reaction is highly 

exothermic and heat generated provides steam for use by let down turbines to drive pumps and to provide process heating. 

The effluent gases are fed directly to an absorption tower. Demineralized water is fed at the top of the tower and formaldehyde solution is collected at the bottom. 

ENVIRONMENTAL ASPECTS Formaldehyde is toxic by inhalation, prolonged or repeated contact with the skin 

or mucous membranes, and by ingestion. It is extremely irritating to the eyes, nose and throat on exposure to concentrations 

ranging from 0.1 to 5 ppm. The OSHA exposure limit is currently 2 ppm for an eight hour time weighted average but a change 

to 1 ppm has been proposed. Formaldehyde is a suspected carcinogen based on demonstration of carcinogenesis in animals. 

It was found to cause nasal cancers in rats after exposure to 15 ppm for 13-16 months. Epidemiological studies of plant 

workers by Ceianese and Du Pont revealed no unusual incidence of cancer. 

To the best of our knowledge the information contained herein is accurate. However, we do not assume any liability whatsoever for the completeness or accuracy of this report. 
«• . ,i * CHEMICAL PROFILE 

FORMALDEHYDE September 18,1989 

SUPPLY 

PRODUCER CAPACITY* 

Alcolac, Seiple, Pa 135 

Borden (12 sites) 2,276 

BTL (3 sites) 285 

Chembond (4 sites) 400 

D.B. Western (2 sites) 90 

Degussa, Theodore, Ala 65 

Du Pont (5 sites) 1,450 

GAF (2 sites) 200 

Georgia-Pacific (8 sites) 1,465 

Hercules, Louisiana, Mo 180 

Hoechst Ceianese, (3 sites) 2,060 

Monsanto, (2 sites) 475 

RVP, White City, Ore 300 

Wright, Acme, NC • 114 

Total 9,495 

'Millions of pounds annually on a 37 percent basis. Du Pont closed its Grasselli, N.J., 

plant at the end of 1988, and plans to move the equipment to its La Porte, Tex., site by 

the end of next year, to supply the company's BDO facility. The move will mean an 

extra 200 million pounds of capacity at La Porte, where capacity was expanded by 30 

million pounds last year. The company started a new plant at Parkersburg, W. Va., in 

the fourth quarter of last year. Monsanto closed its Addyston, Ohio, plant at the end 

of 1987, and will be expanding its two remaining plants by the end of this year, for an 

addition of about 20 million pounds. Georgia-Pacific increased capacity at seven of 

its plants, mostly in the first quarter of this year, for a total increase of 120 million 

pounds. The company is considering building a new plant at Grayling, Mich. Chembond intends to raise capacity at Springfield, Ore., by 100 million pounds, to 300 

million, by the first quarter of 1990. Hoechst Ceianese plans to boost capacity at 

Bishop, Tex., by 100 million pounds, to 1.9 billion, by the end of this year. Borden 

debottlenecked seven of its plants from the end of 1988 to the first quarter of this 

year. The company acquired Perkins Industries' 60-million-pound plant in 1987. 

Degussa entered the formaldehyde business when it opened its plant last year. 

Alcolac is a subsidiary of Interchem Inc., which acquired IMC's formaldehyde and 

other Industrial chemical businesses last April. Profile last published 9/29/86; this 

revision, 9/18/89. 

DEMAND 

1988: 6.73 billion pounds; 1989: 6.5 billion pounds; 1993: 7.6 billion pounds. 

(Includes exports but not imports, both of which are negligible. Last year, 

exports totaled 19 million pounds, and imports totaled 11 million pounds.). 

GROWTH 

Historical (1979-1988): 0.4 percent per year; future: 2.5 to 3 percent per year 

through 1993. 

PRICE 

Historical (1952-1989): High, 10.5c. per pound, 37 percent basis, uninhibited, f.o.b. Gulf; low, 3c. per pound, tanks, dlvd. Current: 9.8c. to 10.5c. per 

pound, f.o.b. Gulf. 

USES 

Urea-formaldehyde resins, 25 percent; phenolic resins, 22 percent; acetylenic 

Continued on Page 47 
«^ 1 

CHEMICAL PROFILE 

FORMALDEHYDE September 18.1989 

Continued from Page 54 

chemicals, 11 percent; poryacetal resins, 9 percent; pentaerythritoi, 7 percent; 

hexamine, 6 percent; urea-formaldehyde concentrates, 6 percent; MDI, 5 percent; melamine resins, 4 percent; miscellaneous, 5 percent. 

STRENGTH 

Polyacetal resins are growing at 5 percent or greater per year. Acetylenics are 

growing nearly as much, led by 1,4 butanediol use in PBT and THF. 

WEAKNESS 

Exports of finished wood products are down this year, resulting in less 

demand for U-F and phenolic resins. Small, direct-application uses of formaldehyde have been prone to substitution, due to safety concerns. 

OUTLOOK 

Overall growth will not exceed 3 or 4 percent. Should the economy falter and 

construction decline, demand for formaldehyde-containing resins will slacken 

further. Formaldehyde remains a highly-scrutinized chemical among regulatory 

agencies, and future action against it is a possibility.