p.1 

OAR Box 1877 

Prepped by Keeia Richards 

Document Number: 

7) II-B-4 

Docket Number: 

A-90-19 

Printed 12/2/200810:36:46 AM Sheet 7 of 46 
P.2 

MEMORANDU M 

TO: Process Vents Docket A-90-19 

A-90 19 

ll-B-4 

FROM: Wanda Floyd 

DATE: October 1990 

SUBJECT: HON NESHAP: Industry Characteristics/ Acetaldehyde 

Attached is a product-process summary (PPS) for the production of Acetaldehyde via air 

oxidation ethylene 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. 

"Chemical Profile" In: Chemical Marketing Reporter. Schnell Publishing Company, Inc., 

New York. May 12, 1986. 

"Chemical Products Synopsis" In: Mannsville Chemical Products. New York, February 

1985. 

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

New York, 1978. pp. 145-150. 

Shreve, R. et. al. Chemical Process Industries, 4th edition. McGraw-Hill Book Company, 

New York, 1987. p. 692, pp. 708-710. 

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

1986. pp. 66-69. 

Austin, George T. Shreve's Chemical Process Industries. 5th edition. McGraw-Hill Book 

Company, New York, 1974. pp. 767-768. 

Kent, James A. Riegel's Handbook of Industrial Chemistry. 8th edition. Van Nostrand 

Reinhold Company, New York, 1974. pp. 936-937. 

1989 Directory of Chemical Producers USA. SRI International, California, 1989. p. 427. 
P.3 

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

December 1980. p. III-l. 

Kirk-Othmer. Concise Encyclopedia of Chemical Technology. 3rd edition. John Wiley & 

Sons, New York, 1985. pp. 7-8. 

"Acetaldehyde." In: Chemical Hazardous Information Svstem (CHRIS). U.S. Department 

of Transportation, 1985. 

EPA-450/3-87-026. "Appendix D." In: Hazardous Waste Treatment. Storage and Disposal 

Facilities (TSDF). July 1990. 

Sitting, Marshall. Handbook of Toxic and Hazardous Chemicals and Carcinogens. 2nd 

edition. Noyes Publications, New Jersey, 1985. pp. 21-22. 

*in. i i fefTfispioiig QiBOty Assurance 

_^_.^ •_*„_ _ 

mm is telef fe A-90-19 

l'B-252 
* 

Q^c\ tyv\ >S\c 

P.4 

f\ 

Preparer: M»/flfc,L>J/ 

Date: r--? ^ 

Reviewer: 

.JHINISTRATIVE NOTES 

Product-eroces* ?fr>?oft 

Hours spent on this PPS 3 ^ s 

P-P Name htifoi-y'^jd,*. V«»--q.-ray.//*hav- of ? U^i 

Incomplete Items (parts of 

form you cannot complete) 

(line # and Ascription) 

£*\<--5 'JM* /7e,w. 7-8 , /a .^ 

Date Cleared Initials 

4 , 

*• 

% 

^ 

Chemicals missing CAS numbers 

£41^1 <^JU 

Plant with CUY but ne County (plant name, dty, state) 

rM 64*j X 

T* 
P.5 

Preparer: A- fto-laac/.' 

Date: r-qo 

Reviewer: 

Chejnical Name 

PRODUCT-PROCESS SUMMARY (PPS) 

/WtH(3*3.^ _ 

• •_*-Xv..v> -. V V i-h'-X 

ooi 

Al tentative epical' mm 

CAS I W? Q 

Karen ffm^ 

CHEMICAL SPECIFIC INFORMATION 

1.0 U.S. Production 2f > Ref # 

A^Ko Al.^_ ^ cltt-AnJ^. D(u>|i A4iiit^< 

5 . P9 ., Ref Year Kfc*-

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

different reference) 

•fifihijjiiilljons of k£)or millions of oallbns j 

* -7 So •" •r-i'-4 

-S7o-:- u < 

zfI 2- 0 

fr^tej hr 1^ 9 HoHo/j/ 

i/Ko3_r i/oanon 

d.<-*W 

y«u Vt_"f iiio'c c 

3 rtf? p r^W »H,«J, T****, <*:'"> 

1.8 Comments 
P.6 

2.0 Chemical End-Use Ref # 3- . Pg # . Ref Year K^ 

JlSfi Percent 

^p- 4

 H % 

A^c,

 (r7 ° 

pewfa*e*/Hi4-ta f<R>] ' ' ° 

1 ei/G.ce-fi<_ HOC * G / o 
3.0 U.S. Producers Ref # XI . Pa # ., Ref Year ftV> 

or millions of gallons 

3.2 Name, Location, and Capacity 

J/^6.5 £-^S//M<5>-« 

Process Used 

(use P-P #) 

CAa^^ C^teJ) ^^'A , , rx 

l^MsaCt/- <a*) y / / / 

AP- ! 

PP-l 

Jnits 10 (^ 

sr^o 

Total Capacity 1^0 7S o 

'»&(*«*• ^i'.-^r'* 

*•>! 
P.8 

PRODUCT-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) 

Name 

p-p l °3 mtJkx :_____. •4*-*%- °- ' 

P-P 2 °^kAtxYko-X a / tfUca.t-0 j 

P-P 3 <9-*^'l\-,ro 2**cJkoYt of- ffla ^ 

4 k}Jr>l]*m »-/ *c-ef)kt 

Ref #_2_ . Pg 

Commercially % Nat'1 

Viable (y/n) Capacity 

/ 3 

P-P 

P-P 5 P"^7/ a ( 0 ft.,'tr't !<'<>•' a r- Lyd raCif lokf 

P-P 6 

4.1 Documentation of P-Ps Excluded 

P-P not 

Commercially Viable 

«/ 

*/ 

/S 

Reasons 

K?t fl«*d Pr?S <W -J fo-Q ^<J C^r^VU^ 

A-CL uitk.i 
P.9 

*&' - 'mmmwBsmpi* **** Ref # lO Pg # NS' 

CS Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylatlon Reaction 

Halogenation Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenat1on Reaction 

Sulfonatlon Reaction 

Catalytic Reformation 

Hydrodimerization Reaction 

Generic Reaction 

CMi-^W ^ 

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

-3 Sfa/*J ^ t'»* "tf*r<«<t 
P.10 

«-hl f-

9u 

4.5 Written Description 

In the left margin, indicate references and page numbers throughout written 

description. 

1 3 , .;•-•-•/-i . /] ^ ^t*cL -shxyu /pVi)f-__SS UJ^'« - pu-d. 6tC-\(^Ut. i-•*, uvV . 73^ -

r«ftcfi>/ i-ffl--**^ i , d^Jc^J a;J uiJtr-*.c,^l*~4. LUts^-kJ. «o.S - 5 r«e^c_W 

t C-c.tt.-y- j^. L <J (^CJUtj.-^eO'-X^y. i' i CO-M^'-C ^ .-• XU 5ft* ^ 1/ coC h) V 

-p ( \ /J 

• 3 oc-fA3f • *•• * ^o-^p* ^ si^fcn*. <Uv,^K^ j-f P^ £l z

 l Cuttle 

(1)

 IU"' •''* 'x

 ""*£•' *****> f' J t ^ ^.^f-**- a^ju* . uJW . «~AtLeJ aK4 / 

(3.33^ f^^Ki . H\--f\*Uy ^k^^^ f,,Jh>v 

£•___ pvA. ^ -fl. p.<_u ^ l»i*.'i</ utf . 3 U-Hn.....« h 

lO^F-/ t 3 *. Wc/3ov^cKv, Ata*kiirk 1 ' ,1 
Separator 

Reaction Gates 

Reactor 

Q) 

Ethylene 

Oxygen 

Water 

Catalyst 

Solution 

_____ 

?(3k) Purge 

CI 

Water 

L 

Air Steam 

Water T 

Acetaldehyde 

Catalyst 

Regeneration 

Section 

P.11 

Acetaldehyde 

Fractionator 

• - Steam 

(___3~ 

Recycle 

Compressor 

Water and 

Heavy 

Impurities 

Pit. 28.13 Acattidehyde by single-rage Wacker process. {Hahn. A. V., Tha Patrochamkal Industry,"p. 243, 

UcQmwHUI, 1970.) 

5.0 Process Flow Diagram (attach at end of package) 

5.1 Flow Diagram Reference: Ref # (r Pg I ?$?* 

5.2 Comments on Flow Diagram 

Component Types 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others . , . *. 

Ref I 

__2_ 

4 

<- . Pg # ? ^ 
P.12 

6.0 Chemical Data 

6.1 Balanced Chemical Reactions Ref # ___[_£__, Pg # )4^> 

c,U,3oz 3 _ > CU^HO 

6.2 Chemical Tree Ref # /3 . pg § /*-/£ 

t 

t%kr " KkA.-yfito* 
P.13 

6.4 Stoichiometry Ref # __3_ , Pg # Q_ 

Show calculations and assumptions and then summarize in table on next 

page. 

UU* ' 'XxO^ - =* C ^ CHO 

m ^10 =* VV 

AcxfVli**^^ 
P.14 

ReA )o ?.t<4S 

6.4 Stoichiometry Conversion Factors 

b •nff$7*ft r for OHftttKt ) H 

d) mMn\tfwmir$* u-mmm 

e) ^^mf^'mtdrWr'C^Pi^ra 

f) Conversion Factor Comments 

<?.<-?? k^kk 

*£ 

> 

• % 

H 
P.15 

6.4.1 Product 

O 'Z6.4.2 Raw Material(s) 

#1 kU^U. .. -

#2 _ 

#3 _ 

#4 _ 

#5 _ 

6.4.3 Co-Products 

#1 

#2 

#3 

H 

1.5 

6.4.4 Bv-Products 

#1 /AH/M / n>ptAt<i -Ag-'S 

#2 ; 

#3 ; 

#4 , 

#5 

6.4.5 Intermediates 

#1 

#2 

7 fo-j-o 

37 srzv-^7 

o. c 

o.V 

ft? dfl^ fu? dp>S .3 iKa--
P.16 

7.0 Process Vent Emission Sources 

7.! Are there process vent emissions! 

C»*5 ^U-P-Zf 

(Y/N) 

7.1 kit Oxidation vent emissions? )/ (Y/N) Ref # , Pg # °l2? 

7.3 Comments Ref I ., Pg # 

tf (Y/N) Ref # _£_, Pg # _ 

7.5 Comments Ref I ., Pg # 
P.17 

7.C \JM 

7.7T^iH^rpfJ®^pii 

Ji (Y/N) Ref # 

•\ *>\<~aj 

li il l 2-. Pg * 

(Jl\y A) 

73 »ttilpr;igr'IW#;v^pi 

7.9 Comments 

•J^^^^^W^T" 

lUnXS.-**, i^uJ " vMC*-w*v>, J_ 3 ( / 

^~- ft 

3 

Ref # , Pg # 

I 
P.18 

8.0 Transfer Emission Sources Ref # , Pg # m 

8.1 ft*Prldtttts/Co-Products Transferrer! > (Y/N) 

8.2 What materials tre transferred! 

8 . M Product 

8.2.2 Co-Products 

I 

8.3 Comments Ref # , Pg # 
P.19 

9.0 Storage Emission Sources Ref # , Pg # 

9.1 AhtlMOTfaTi store^l ^ (Y/N) 

9.2 What materials are stored? 

Storage Service 

9 t M PrQdqct . , / w / -f 

9,2,2 C9-Pr9dgcts *<-e/;e ^-^ 

/ 

9,2,3 Raw Material? , , 

9.4 Comments 
P.20 

/ lyi 

10.0. Wastewater Emission Sources Ref # 6 pg # '__ 

•••••••••• I < (VN) 

10.2 Describe wastewater 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

#1 

#2 

#3 

v/^U wol-tY /.-0o, sf'rippe.r 

10.3 Stream Composition Ref # , Pg # 

(provide only if readily available) 

Stream #1 ^ J^JJA Steam #2 

Organics Organics 

HAPs • HAPs 

Water Water 

Other _ Other 
Stream #3 

Organics . 

HAPs 

Water 

Other 

P.21 

10.4 Comments Ref I ., Pg # 
P.22 

[Vcrry, ll-sti; ll^-Zif.v > ~%y<Lfor -+-t_r 

CHEMICAL PROFILE 

; 

From the Bookshelf ?>£ 

Acetaldehyde ,*:, 

SUPPLY "-' 

PMOUCSR CAPACITY* 

CiUnin.BayCTy.Tti 22S 

, Langview, Tm 47» 

Total. 700 

i of pound* par year. Cslanaaa's <80 iWo n pound par ya r pfeM al 

Clear Lata. Ta»_, haa baan Wa sine* 1M1. Prafla laat publalted 5/30/13; tt* 

ravMon,S.12/M. 

DEMAND 

1988:650 million pounds; 1988:650 minion pounds; 1990:650 

million pounds. 

GROWTH 

Historical (1978-1988): minus 3.9 percent per yea. future: flat 

through 1990. 

PRICE 

USES 

Historical (1982-1988): High, 37%c. per pound, tanktrucks, 

dh/d.; low, 6c. per pound, same basis. Current 35Vic. to 37V_c. per 

pound, same beale. 

Acetic add, 50 percent; exports, 14 percent mlscelaneous, 

including lactic add and crotonaldehyde, 13 percent; pyridine and 

pyriudlne basse. 8 percent; pentaerythrttol, 7 percent; peracetic 

STRENGTH 

Exports remain strong, particularly to Mexico, totalling over 80 

frtHon pounds last year, up from about 65 mMion pounds in 1983. 

WEAKNESS 

q^acitti ii-jizatton is expected to be about 50 percent this year 

because of therepBEbment of acetaldehyde oxidation by methanol 

carbonylation over the last several years. 

OUTLOOK 

Acetic acid demand may decline through 1990 should Eastman 

decide to expend its coal gasification ptvtt The expension, if decided upon, would be in place prior to 1991 and would subetantialy 

_-4____a__a____________> _i^^Ha*_____Hu*d Jtf^ v ____*_____!___ _•_______! !___. »_•__________. ^^^^k^^^^^ A _____________ y^^A^*^ 

oecreese oemana rar aceoc acn n aceoc arwiyonue praoucoon. 

As slight growth is expected for end usee such pentaerythrttol 

and pyridinee, minima, growth in acetaldehyde demand can be 

expected If Eastman opts not to expend its coal gasification plant 

Corrosion Control 

Covering tbe fundamental coocepti, techniques and technology of corrobn, 

this book* is presented as an aid (or all practical engineers in the process* 

whether their background is in chemical, civil or mechanical engineering. 

It deals with corrosion phenomena and their mechanisms, attributes of 

materials and their corrosion characteristics and tbe corrosive nature of 

environments. The information presented is intended to help the rngintti ant*** ! 

correct corrosion problems but to prevent them at the start by selecting the***'*! 

material and using modern corrosion technology in design and application. *^**H 

A recent estimate of the total cost of corrosion in the US puts the figure at a s__ 

WO billion per year. Of this amount, perhaps f 55 billion is irreducible. The autbw* 

out that the breakdown of materials because of corrosion cannot always be avoided* 

is it always economical or desirable to do so. It ia assumed well-engineerad rr___ 

already represent tbe optimum combination of construction materials and apptwilz 1 

corrosion control measures. Thus, barring technology breakthroughs there is DOWS?" 

ity for further economies. For example, the corrosion of some equipment (toSe i 

lifetime of an acetic add plant is regarded as simply one of the costs of doing b^W* 

•CORROSION CONTROL IN THE CHEMICAL PROCESS INDUSTRIES. ^ ^ 

By C. P. Dillon. Cloth. 109 pages. UQ laches. McGraw-Hill Book Company, New York. N.Y m 

Federal Biotechnology Activities 

This book* presents an overview a_ .>.•_ -fith specific information on tbe | 

Federal policies, issues and research in i-i*. chnotogy that pertain particularly to • 

agriculture. Tin US government has cv"»' Table Involvement and funding in bj___^. ' 

oology research, and is continuing to an..*tonae the need for this research intht-yn^j 

already involved in agricultural research along with the agencies that have "plrilfa ' 

related programs. 

The book urges that US government policies aad issues be resolved in such a way ia_r j 

government, universities and industry can work together in order to achieve viable ag ' 

productive results. Additionally, it is felt there must continue to be Federal rem-**-^ . 

support in this Held along with private research in order to enhance potential _* 

commercialization. Hopefully, this will help the US to find solutions to worldrfe-- ij ^ 

problems, increase agricultural trade aad enable the nation to continue to tarn . 

leadership in the new and exdting biotechnology industry. 

•PLANT AGRICULTURE, FEDERAL BIOTECHNOLOGY ACTIVITIES: By Carolyn Block. Cad* J 

210 pagaa.« X »Vt Indus. Noras Publications, Mill Road at Grand Avenue, Part Ridge, NJ. tri**" 

119. 

Jhe Chemistry of Glass 

This book* presents data oo a relatively young branch of chemistry, compri_i_gft*) 

boundary area between chemistry, physics, mineralogy, biology and, recently.i 

aa welL The field represents a special branch of-high-temperature chemistry ia i 

chemical processes of transformation of matter take place and has led to some r 

over the past twenty yean that would hardly have been believed possible befora 1 

thermore, it is likely glass and silicate chemistry will assume even more impartaneal 

mankind at the tun of the century u classical sources of raw materials — oil i 

gas and ores — begin to be depleted as a basis for material development and f 

The volume has been conceived as a text for university-level students of (__• a 

and industry. Its content is largely the core of a course at the Friedrich-Schilkrl 

slty in Jena, West Germany, offered since INI and updated annually. In soneer 

book goes beyond educational needa and thus might be useful to those already I 

the Held. 

•(^EM__rniYOPGI-__&ByW.VotilTrisrtaUdbyN.Krtk_tCV)t__J_Sp-g«»«Xlti 

American Ceramic Society, Int. Coimhaa, Otrto. IM. 

MEETINGS 

CALENDAR 

May 1-L.19M 

THIS WEEK 

*"WCA * OfcCMMTS SCCSm. 77»l wn_d 

•id axpoeson. Jo-Wi* wah Japan QS 

mi. HBHn Ha-Mlan HO******, Hrou*! Hmmt. 

.-IS. 

s<iawiai*nowaL-WTTTVTio>sywi>_iiiL 

mooucnsi ZTfi 

Argman_.M_»-_-1«. 

THU MONTH 

ion oonNranoa on naeda lor good tdsnoaln 

Don aid ragjJaaon. Hyan RagwcrCapaol m 

Wa_**g_»i.0.C:.Me*-_2. 

«CAM aermvri or CMoarra, _m_* 

MACT* 82nd 4vw»vfll frmMfiQt Wy-ntf-m FrmMn 

Ptaa How. mesapaa. Pa.. Mar 17-ai. 

NOHTMBASTIIM ocaacM. ASSOCUHCM, tm annua Spring _pona autog, Saartaw Couwy CM). Ab-

_____ M l Umyjf 

TtXVkM ASSOCMTKM OP TW PU_> « W M m •*• 

oortwr.^couia . Twang NonJHowna. Equip. 

nwa wd Aoaeduae." ffaadelpMB Coaaga of Tv* 

t_MVdSc__noa.PMad^hlal ^L . May27<2B. 

JUNB 

WWIC«N ASSOCUTION or SNAIL MJSAAOI 

NATIONAL ASSOCIATION OP PMAJWSACHmCAL 

MAMjPACTW-M, ntt -war musng ma -rtm. 

WsmsvHBKh wntnttiiintt, \\ dnjQ tiJNwttainQi 

Hyatt %gn y Hoe* (CryeM cay). Aieigan. Va, 

Jul* 17-18. 

LATER ON 

M__MC«NS«mvriCI>CMS__KALB«_M__nia.a«-

mm..mmi u^^^^m. _^_____aa___B aj^^ ^ ______H ^ _E1__ a__M_____a_k____p 

nUB VVajfaw TaOT^t MV I DIBvV ^* . nwMnTOV 

2-7. 

oj)r<at^^woo>po_*wton>t riwntwf HOMI WP-B^ 

wednii »amia How. N— ran. »•" " 

COtMCSL K N CWMCAL WSBAIIOi anf ' 

MjIMnOK • 

oonMranea. kaarrloit HoM. Sadda Break, N^., Juia 

18-ia 

maaang, Oraaremr HoM iMMi Siesw Sprtigt. W. 

Vi-L^Juia^f ^ ^ 

ATMM, OWtfMM '« 

O'Hm. nnaamoni. a., JU M 13. 

nmuiS R aajnTWTt. isss -ranaang oartwwa. 

Vtt Onartnar, mm MH w Springs. W. Va.. Juia 

9-11. 

HIMMNCSIraWBATHN, nu t raoognMon aoarda 

oontwioa. wadort^siorta HoM. Naw Yorii. A_ia 4. 

MSnrUTI W TOOO TSCMCUOMTS, 40(1 amual 

maaang. tMtm Comanaon Onr . OSa, Ta».. Juw 

__^ M a____.^_> __ _M__b ___. .____.^_a ^<____.^y ^tak. 

lyooH mt/ntQOKtMtt, fottwf M I MWKW I wivncs a***. 

cMy aid SocMy tor A«p_tf Spacasaoapr. Maw York 

(•on HeMlNw Yarti Oaoear 2M4. 

Aa__ncAN aenmauM avrmiri, avui maaang, 

San Frinrtan CUT.. N8mitear»11. 

etittaum cHPecat moouews tmootmtm. 

-itw*na__n_l si^iipoahjni om__n_povt_a_n wnvgv^f 

mtotm. Vanooun*. S.C.. Canada, 3ap»i_» 1*-

18. ____ , ._ _ 

wflV. VIS ttyffwC-M 

t (^MtaVOI tt9 AflWlOMI 

' ""^.Ownaealinbuaay wtiamW 

tfw w¥ortfl li 1 Qdnj?*'. Htwpofitt Rttoft How, NPW» 

pan Baaoo, Ca*.. SapwmOw 7-10 

MWN. 7*0 -nua maaang. Marion's Hweor Saaon 

Nw»OH__ilu*Waa,-J.W.M«iluUlW-* 

•MOSIMI HTMCMSMC*L aSSOCMtOll 

naaang, laonta Cwlo. Monaaa S«aa«* ^ 

bar 1: dkattudon maaang. Oooow iM * 

MRTum MMJNO r«au, iaas <««•« -

HOWeeenora.Md..NOMnaariTji* figH f 

HUORAICa raUNDAIKM I M Mma*»" 

— a . "Tho Ps-KHaogy ol PwtoiwY- **~,*fJ 

wwwa oawaory nnnim aww 1 < ^ " 

^^^^J^^^^a . 

mt^.<ar*mm-SaM.y*y*•mJ?DZ^

, 

PIMM Engnaara. Qaoqta worid CoV * 

*«r«_.(__..Oe__0wa-10. ...«Mf0 S 

TUn U ASSOCUTION Cf T « W ""XxP* 

OUeiWY. isss potyman. ana«wjj|rr 

UJINIWUM and sada tm. Oonaa" " ^ 
&€»Ut*l PttdvU S^Af4 *—c£ffiSSS£ 

FEBRUARY 1985 Cortland, New York 13045-0230 

Previous Report — January 1983 ACETALDEHYDE 

FOCUS....Acetaldehyde is an organic intermediate or building block chemical which has lost position in the 

US and most other parts of the world for the synthesis of a variety of major chemicals. Acetaldehyde was 

once used commercially as a raw material for acetic acid, butyraldehyde, glyoxal, glycerin, and vinyl acetate monomer. Although Eastman can still produce significant quantities of coproduct acetic acid from acetaldehyde, all of these major chemical commodities are currently synthesized directly in the US from 

other raw materials and processes which are generally more economic. 

Acetic acid, produced by the liquid-phase oxidation of acetaldehyde, was previously the dominant derivative of acetaldehyde. Methanol carbonylation is currently the most widely used technology for acetic 

acid synthesis. Some acetic anhydride, a derivative of acetic acid, is now produced by Eastman by carbonylating methyl acetate with carbon monoxide. With the new processes, Celanese and Eastman placed units 

producing acetic acid by the oxidation of acetaldehyde on standby. Acetic acid made from acetaldehyde is 

not competitive with material made from low cost methanol, .except where the acetaldehyde may be derived 

from subsidized fermentation ethanol in countries such as Brazil. Under certain market conditions, Eastman's coproduct acetic acid made from acetaldehyde used as a co-oxidant in terephthalic acid manufacture 

can be competitive. In the Eastman process, paraxylene is oxidized to terephthalic acid and acetaldehyde 

is oxidized to acetic acid. The acetic acid is recovered rather than decomposing to carbon dioxide and 

water. 

In the US, solvent esters are the second largest derivative of acetaldehyde. Texas Eastman produces 

ethyl acetate from acetaldehyde by dimerization. This ethyl acetate synthesis is novel in the US but is 

more widely used elsewhere in the world. In a related synthesis, Eastman also produces isobutyl acetate 

via acetaldehyde. 

Pentaerythritol, pyridines, and peracetic acid are major derivatives of acetaldehyde which have had 

static or declining growth patterns in the US in recent years. Lower volume derivatives such as 1,3 butylene glycol, lactic acid, crotonaldehyde, and chloral are also mature commodities. 

In addition to the end of on purpose acetic acid production in the US, glyoxal, vinyl acetate, glycerin, and butyraldehyde are no longer produced from acetaldehyde. 

The attrition in derivative manufacture and demand stagnation in major end uses has probably reduced 

US demand for acetaldehyde to the range of \ billion pounds. Demand for derivatives other than coproduct 

acetic acid has probably dropped below 250 million pounds per year. 

OUTLOOK....Future US acetaldehyde consumption will remain relatively static at about 450 million pounds 

per year unless acetic acid markets require increased production. US exports of acetaldehyde to Canada are 

expected to continue at a rate of about 10 million pounds per year. Exports to Mexico will depend on future Pemex output. US exports to Mexico supplement production by Pemex. 

The pyridine requirement could decline further either because of foreign competition or replacement 

raw materials. Acetaldehyde is the best raw material for pyridine and the picolines, but technically many 

other chemicals will produce pyridine if reacted with ammonia. Acetaldehyde is thus always*vulnerable to 

replacement by some other chemical in this application. 

PRICING....The US merchant market for acetaldehyde is concentrated in a small number of buyers of large 

quantities used to produce pentaerythritol, pyridines, peracetic acid, and other derivatives. Except for 

minor quantities, merchant market sales are at negotiated prices which are considerably below the published list price. Because of the limited number of producers and major customers, actual pricing is proprietary and confidential. y 

AVERAGE PRICE RANGE - ACETALDEHYDE 

Cents Per Pound - Freight Allowed - Tanks - Eastern 

1960 

Trade List 10 

PPLY AND DEMAM)... 

1960 

Capacity na 

Production 1000 

Exports 

Demand 1000 

1965 

10 

•Millions 

1965 

1600 

1200 

1200 

1970 

9 

1975 

16 

of Pounds.... 

1970 

20d0 

1600 

20 

1580 

1975 

1500 

1000 

60 

940 

1980 

28 

Estimated. 

1980 

Tvioo 900 

120 

780 

1982 

331 

1983 

35? 

...Domestic US 

1982 

800 

650 

35 

615 

1983 

800 

700 

60 

640 

1984 

""37? 

1984 

750 

650 

95 

555 

1985 

37 

1985 

750 

630 

120 

510 

1986 

"37 

1986 

450 

1988 

39 

1988 

480 

1990 

41 

1990 

480 

All data is estimated. US Government sources do not separately report production or 

exports of acetaldehyde. Exports are principally to Mexico. Imports, less than \ 

million pounds in 1984, are separately reported by the Bureau of Census. 

AVAILABILITY....Current US effective operating capacity for acetaldehyde is between 700-800 million 

pounds. In addition, an estimated 600 million pounds of capacity at the Celanese plant at Clear Lake, TX 

has reportedly been on standby since 1982. 

Because of high acetaldehyde export demand and the somewhat unexpected need for producing acetic acid 

from acetaldehyde as a coproduct of terephthalic acid, effective capacity has operated at a rate over 80S5 

for the past few years. It is anticipated that the US acetaldehyde operating rate will drop well below 70S 

for the balance of the 1980's unless supplemental acetic acid is again unexpectedly required. 

Ethylene and derivative acetaldehyde have been readily available in Europe at competitive prices. This 

has had the effect of reducing US acetaldehyde demand since some derivative manufacture, such as pyridine, 

has reportedly been transferred to facilities in Europe. 

In Brazil, Coperba increased acetaldehyde capacity to 60,000 metric tons/year by early 1984. This material will be used locally for derivatives manufacture or may be exported. 
P.24 

PRODUCERS AM) CAPACITIES - ACETALDEHYDE - MILLIONS OF POUNDS 

PRODUCER LOCATION 1985 CAPACITY 

Celanese Chemical Bay City, TX 250 

Texas Eastman Longview, TX 500 

TOTAL 750 

Based on trade estimates. Celanese also has 600 million pounds of idled capacity at 

Clear Lake, TX. Pemex has 200 million pounds of capacity at La Cangrejera, Mexico. 

END USES....Acetaldehyde, also known as acetic aldehyde, ethyl aldehyde, and ethanal, is a clear colorless, highly volatile liquid with a pungent odor. It is flammable and highly reactive. Acetaldehyde is 

readily oxidized to acetic acid or reduced to ethanol. Aldol condensation forms crotonaldehyde and higher 

aldehydes such as 2-ethylbutyraldehyde and related compounds. The aldol reaction of acetaldehyde and 

formaldehyde yields pentaerythritol. It condenses with phenol or urea to form thermosetting resins for 

varnishes and enamel oils. With aromatic and aliphatic amines, it forms dyestuffs and rubber chemicals. 

Until replaced by more economical carbonylation processes, acetic acid was the major derivative. In 

the mid 1970's, acetic acid production accounted for about 2/3 of US acetaldehyde consumption. Eastman 

still produces acetic acid as a coproduct of terephthalic acid using acetaldehyde as the co-oxidant. The 

process is flexible and Eastman can maximize acetic acid output to meet internal and market demand. 

Depending on Eastman's rate of operation, acetic acid via terephthalic acid may account for between 30 to 

6055 of total domestic demand for acetaldehyde. 

Ester production, particularly ethyl acetate and isobutyl acetate, is currently the second largest 

outlet. Eastman produces esters at Longview, TX from acetaldehyde. the Tischenko process involves the 

liquid-phase dimerization of acetaldehyde in the presence of catalytic amounts of an aluminum alkoxide, 

activated by anhydrous aluminum chloride. 

Pentaerythritol manufacture accounted for about 10S. of US acetaldehyde consumption in 1984. Pentaerythritol is a solid polyol used principally to make alkyd resins for protective coatings. Rosin esters 

and acrylate esters based on pentaerythritol are also used for coatings and inks. Other pentaerythritol 

esters have application in synthetic lubricants and specialized fluids. It is also a raw material for the 

explosive PETN (pentaerythritol tetranitrate) used chiefly as a booster for TNT. 

Pyridine chemistry also makes up about 10% of demand. Acetaldehyde is reacted with formaldehyde and 

ammonia to produce pyridine, methyl ethyl pyridines and picolines. These chemicals have many uses, including surfactants, pharmaceuticals, and plastics. 

Acetaldehyde is converted to peracetic acid which gives up its peroxygen atom to double bonds, producing epoxides, with acetic acid as a coproduct. The largest use for peracetic acid is as a raw material for 

epoxidized oils, used as plasticizers. Epoxidized soybean, linseed and tall oils are also produced using 

hydrogen peroxide. Union Carbide continues to use a peracetic acid route for plasticizers and resins. 

Other significant derivatives of acetaldehyde include 1,3 butylene glycol, crotonaldehyde, lactic acid 

and chloral. Celanese produces 1,3 butylene glycol. Eastman aldols acetaldehyde and dehydrates the acetaldol to make crotonaldehyde. Monsanto reacts acetaldehyde with hydrogen cyanide to make acetaldehyde cyanohydrin (lactonitrile) which is subsequently hydrolyzed to lactic acid. About 5 million pounds of acetaldehyde are converted to chloral for use as a raw material for DDT for approved applications. 

END USE PATTERN - 1984 ESTIMATE 

DERIVATIVE PERCENT 

Acetic Acid (via terephthalic acid) 

Esters (includes ethyl acetate) 

Pentaerythritol 

Pyridines 

Peracetic Acid 

Other 

55 

10 

10 

10 

5 

10 

MANUFACTURING....In the US and Mexico, all acetaldehyde is now produced by direct oxidation of ethylene. 

Until the introduction of ethylene oxidation processes, most acetaldehyde in the US was made from ethanol. 

Small amounts of acetaldehyde were also previously produced in the US and elsewhere by the vapor phase 

oxidation of propane. Overseas, in Europe particularly, acetylene has been used as the raw material. 

Because of the better economics of direct ethylene oxidation, acetaldehyde production from ethyl alcohol declined rapidly in the late 1960's/early 1970's in the US. During the period, US ethanol was derived 

from ethylene. In recent years, fermentation derived ethanol has become an important raw material for 

acetaldehyde in Brazil. Low cost or subsidized fermentation ethyl alcohol may become a long term raw material source for acetaldehyde in other countries by vapor phase catalytic oxidative dehydrogenation. 

In the direct oxidation of ethylene, process variations can use oxygen or 

air. The choice depends on local conditions such as oxygen cost, utility prices and ethylene 

purity. The Hoechst-Uhde process employs a catalyst solution of copper chloride containing small quantities of palladium chloride. In the reaction, ethylene is oxidized by palladium ion. Palladium chloride is 

reduced to elemental palladium and HCl and is re-oxidized by cupric chloride. During catalyst regeneration, the cuprou8 chloride is re-oxidized to cupric ion. Titanium-lined equipment is used because 

reactions occur in the presence of chloride ion. The acetaldehyde produced is condensed and scrubbed with 

water from unreacted gas which is recycled. Crude acetaldehyde is separated from byproducts and water by a 

two-stage distillation. 

ENVIRONMENTAL ASPECTS....Liquid acetaldehyde is a skin and eye irritant. Vapors irritate mucous membranes. 

Exposure to high concentrations of vapor can induce narcosia. The 1984/1985 recommended ACGIH threshold 

limit value ia 100 ppm for a time weighted average. Acetaldehyde is on the EPA list of suspected hazardous 

air pollutants. 

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. 
P.25 

&6&*Ucal PitutucU Si^/UU 

Subscription for: 

Radian Corporation 

7K4HH.yUrtljU Chemical Products 

Box 232 • Cortland, New York 13045 • (607)753-8700 
Klaus Weissermel 

Hans-Jiirgen Arpe 

Industrial 

Organic Chemistry 

Important 

Raw Materials and 

Intermediates 

Translated by 

Alexander Mullen 

Verlag Chemie • Weinheim • New York 

1978 
ammoniurn 

a

" citable 

Jnd70-| 0 „ 

''ymersand 

i(ed. for ex-

-fibers. The 

c

 syntheses, 

vith NH, 0 r 

• ^ n also be 

there was still a manufacturing capacity (world-wide) of 

-> 64,000 t'a acetaldehyde. mainly located in Eastern bloc countries, based on acetylene. In W. Germany, approx. 350,0001 of 

acetaldehyde were manufactured in 1976 using primarily the 

ethylene-based Wacker-Hoechst process. Veba is the only 

company possessing a plant (80,000 t/a) for the dehydrogenation of ethanol. 

The available production figures for acetaldehyde in the most 

important industrial countries are summarized in the adjacent 

table. From 1974 onward the US figures are no longer available; however in 1975 the production capacity amounted to 

approx. 730,000 t/a. 

\JO|P^ 

7.3. Acetaldehyde 145 

acetaldehyde production (in million t): 

1973 

USA 0.64 

W. Germany 0.37 

Japan 0.61 

W. Europe') 0.52 

n.a. = not available 

1974 

n.a. 

0.43 

0.58 

0.60 

1975 

n.a. 

0.27 

0.52 

0.40 

1976 

n.a. 

0.35 

0.62 

0.50 

') estimated 

dehyde has 

ongly influedstock and 

role in the 

lydration of 

ermany and 

-al policy. 

igtheoxidad degree. In 

ion resulted 

ig of natural 

lopment of 

ioechst on 

ly replaced 

7.3.1. Acetaldehyde via Oxidation of Ethylene 

7.3.1.1. Chemical Basis 

The principle r»f the ***-rn_*e ss currently in general use - tfre 

partial oxidation of ethylene to acetaldehyde - is based on the 

observation made by F.C. Phillips back in 1894, showing that 

platinum metal salts stoichiometrically oxidize ethylene selectively to acetaldehyde while themselves being reduced to the 

metal. However, industrial application was first possible after 

the decisive discovery by Wacker of a catalytic process using a 

redox system and the development of suitable technological 

operation by Wacker and Hoechst. 

The total process, developed by Wacker and Hoechst between 

1957 and 1959, can be summarized as an exothermic catalytic 

direct oxidation: 

manufacture of acetaldehyde from 

ethylene: 

via partial oxidation on noble metal catalysts 

combined with a redox system 

ISA, Great 

'tal acetalt amounted 

600,000 t/a 

cetaldehyde 

ivde, which 

"een disconie were shut 

ly manufacver, in 1976 

H2C = CH2 + 0.5O,'M'

c

"'"'''CHiCHO 

_W_ > 

58kcal 

"243 y 

/moA (30) 

The catalyst is a two-component system consisting of PdCl2 and 

CuCl2. PdCl2 functions as the actual catalyst operating via 

ethylene complex formation and ligand exchange. The essential 

partial steps in the mechanism are regarded as being the formation of a rt charge-transfer complex, rearrangement to a o 

complex and its decomposition into the final products: 

.principle of Wacker-Hoechst direct oxidation process*. 

homogeneously catalyzed, via -x-o-Pd;® 

complexes, very selective oxidation of 

H2C=CH2 to CHjCHO 
146 7. Oxidation Products of Ethylene 

characteristics of oxidation mechanism: 

intramolecular transfer of OH ligand of Pd 

to ethylenic C. i.e. total aldehyde oxygen 

derived from aqueous medium 

Cl. ,OH 

Pd 

cr \ 

H2C* 

-iO 

CH_ 

Cl -i© 

Pd-C2H4OH 

Cl 

(31) 

CH3CHO + Pd° + 2 Cl® + H® 

CuCU reoxidizes Pd° to PdCI: and is itself 

simultaneously regenerated to the divalent 

oxidation state 

CuCU reoxidizes the zerovalent palladium to the divalent state. 

Although numerous other oxidizing agents can also convert Pd° 

into Pd2®, copper is advantageous as redox system, because it 

can readily be reoxidized from the monovalent state to the 

divalent state with.02. 

The previous net equation summarizes the various reactions 

taking place. They can be formally divided into the rapid olefin 

oxidation: 

H2C = CH, + PdCl2 + H20 -. CHjCHO + Pd + 2 HCl 

and the rate determining regeneration: 

(32) 

Pd + 2CuCl2 r* PdCl2 + 2CuCl (33) 

2CuCl + 0.5O2 + 2 HCl -. 2CuCl2 + H20 (34) 

The rate of both partial reactions can be regulated with respect 

to each other by adjusting the HCl content, the regeneration 

being accelerated by a higher HCl concentration. 

Thus, the required quantity of palladium salt for the selective 

oxidation of ethylene can be limited to catalytic amounts by a 

large excess of CuCl2 (cf Vinyl Acetate from Ethylene, Section 

9.2.1.2). 

industrial operation of two-phase reaction 

with corrosive metal salt solutions at pH 

0.8-3 preferably employs bubble column 

constructed with corrosion resistant 

material 

7.3.1.2. Operation of Process 

The industrial manufacture of acetaldehyde ensues in a twophase, i.e. gas/liquid, system. The gaseous reaction components, 

ethylene, air or 02, react with the aqueous catalyst solution in a 

titanium or lined bubble column reactor after acidification with 

hydrochloric acid. 
7.3. Acetaldehyde 147 

(31 

-nt state, 

wen Pd" 

ecause it 

e to the 

reactions 

•id olefin 

HCl 

(32) 

(33) 

(34) 

h respect 

neration 

selective 

mts by a 

. Section 

Two process variants have been developed at the same time: 

1. Single-step process - in which the reaction and regeneration 

can be conducted simultaneously in the same reactor. 0 : is 

employed as oxidizing agent. 

2. Two-step process - in which the reaction and regeneration 

take place separately in two reactors. In this case, air can be 

used for the oxidation. 

In the single-step process, ethylene and 0 : are fed into the 

catalyst solution at 3 bar and 120-130°C. 35-45*7. of the 

ethylene is converted. The resulting heat of reaction is utilized 

to distill off acetaldehyde as well as water from the catalyst 

solution, which must be recycled to the reactor. By this means 

approx. 2.5-3.0 m3 H:0/t acetaldehyde are recycled. It is 

necessary to use a pure 02 and ethylene (99.9 vol.-%) feed in 

order to avoid ethylene losses which would otherwise occur on 

discharging the accumulated inert gas. 

In the two-step process, ethylene is almost completely converted using the catalyst solution at 105-110°C and 10 bar. 

After reducing the pressure and distilling off an acetaldehyde/ 

H20 mixture, the catalyst solution is regenerated using air at 

100 °C and 10 bar in the oxidation reactor and then recycled to 

the reactor. Since the 02 in the air is thereby largely removed, a 

residual gas with a high N2 content is obtained which can be 

used as an inert gas. The advantages of the total ethylene 

conversion and the application of air contrast with the disadvantages (greater investment arising from the double reactor 

system at higher pressure and the catalyst circulation). 

In both processes the aqueous crude aldehyde is concentrated 

and purified from by-products such as acetic acid, crotonaldehyde and chlorine containing compounds by a two-step 

distillation. The selectivities are almost equal (94%) in both 

cases. 

In 1978, the world-wide capacities of the plants operating according to the Wacker-Hoechst process were approx. 2.6 million t acetaldehyde. 

two variants are possible: 

I single-step process, reaction and regeneration in same reactor, i.e. O, and C:H4 

keep catalyst in a stationary, active state 

2. two-step process, reaction and regeneration in separate reactors with exchange of 

catalyst charge (active and inactive form) 

characteristics of single-step process: 

incomplete C,H4 conversion requires recycling of C,H4, i.e. C;H4 and 0 , must be 

largely free of inerts 

characteristics of two-step process: 

total C2Ht conversion allows higher share of 

inert components, regeneration with air 

saves air fractionation plant, but catalyst circulation consumes more energy than gas recycling method 

higher investment costs because of double 

reactor set-up 

isolation of acetaldehyde via two-step 

purification: 

1. separation of low boiling substances 

(CHjCl, C2H5C1, C02, C2H4) 

2. separation of high boiling substances 

(CHjCOOH, CH3CH=CHCHO, 

ClCH2CHO) 

expansion of Wacker-Hoechst process: 

world-wide capacity - approx. 2.6 million 

t/a (1978) 

in a twoinonents, 

:utionina 

ition with 

7.3.13. Development Trends 

The major amount of acetaldehyde (depending on country 

approx. 50-70%) is processed to acetic acid and acetic anhydride. Therefore each variation in the acetic acid market must 

affect the acetaldehyde situation. If another more economical 

CHjCHO is economically very closely 

bound to AcOH as its main secondary 

product 
148 7. Oxidation Products of Ethylene 

c> CH3CHO converted to AcOH: 

Western Europe 1970 

USA 1974 

Japan 1974 

69 

50 

58 

other AcOH manufacturing processes can 

therefore affect the CHjCHO production 

e.g. high and low pressure carbonylation of 

CHjOH as oil independent AcOH processes 

or other acetaldehyde processes with: 

I. cheaper feedstocks, e.g. ethane (Lummus 

process) 

. simpler operation of process, e.g. by 

heterogeneously catalyzed C,H4 gasphase oxidation (UCC process) 

acetaldehyde manufacture from ethanol according to dehydrogenation principle with 

two process variants: 

manufacturing process for acetic acid should gain in importance 

in the future, this would have an unavoidable effect on acetaldehyde manufacturing capacity. 

fPr. 

ab 

Such economic pressure could be exerted by the carbonylation 

of methanol, since synthesis gas represents the net raw material 

base (cf. Section 7.4.1.3). 

Processes employing ethane directly, instead of the more valuable ethylene, to manufacture acetaldehyde - e.g. in 

CuO-CuCl2 melts (Lummus) - could also be of interest, if these 

processes can be industrially operated under economic conditions. Alternative processes such as the gas-phase oxidation of 

l ethylene on heterogeneous catalyst systems, e.g. based on 

I Pd-V205 (UCC), have not found any industrial application up 

I until now. 

7.3.2. Acetaldehyde from Ethanol 

Analogous to the manufacture of formaldehyde from 

methanol, acetaldehyde can be obtained by catalytic dehydrogenation of ethanol: 

C2H5OH -££!••> CHjCHO + H2 (\H . 

20kcal, ,\ 

+

 84kJ

 /mo 1 

Ift : 

of 

hycl 

dat 

(35) 

I n t 

int: 

mix 

cat* 

atui 

tion 

ing 

vers 

proCO 

1. endothermic dehydrogenation favored 

with Cu metal under H2 formation 

2. exothermic oxidative dehydrogenation 

with Ag metal under H2 0 formation 

to I: 

ethanol dehydrogenation with process 

characteristic: 

limitation of conversion via temperature 

regulation 

In contrast to the methanol manufacture, an oxidation is not 

used as an alternative. Instead, two modifications of the dehydrogenation are customary: 

1. Dehydrogenation on silver, or preferably copper catalysts, as 

well as: 

2. oxidative dehydrogenation with silver catalysts in the presence of oxygen. 

Tol: 

In the USA, for example, the dehydrogenation of ethanol is 

mainly conducted on Cu-catalysts activated with Zn, Co or Cr. 

A frequently applied process originates from the Carbide & 

Carbon Corp. 

The temperature is regulated to 270-300 °C so that the ethanol 

conversion is limited to 30-50%. By this means an acetalAcc* 

the 

prop 

phas 

catai 

at 41 

oxid 

7.4.1 

15-: 

mair 
7.3. Acetaldehyde 149 

rtance 

1

 acetdehyde selectivity of approx. 90% can be attained. The byproducts formed are ethyl acetate, higher alcohols, and 

ethylene. The simultaneously resulting hydrogen can be directly employed for hydrogenations on account of its purity. 

lation 

aterial 

- valu-

•ga in 

fthese 

condition of 

ed on 

ion up 

dehy-

(35) 

is not 

dehvtf 

£ *•*. 

-**" . 

- * < 

To 2: 

If the dehydrogenation of ethanol is conducted in the presence 

of air or oxygen, the concomitant combustion of the resulting 

hydrogen supplies the necessary heat of dehydrogenation (oxidative dehydrogenation or autothermic dehydrogenation): 

I 

C2H5OH + 0.5O2- • CHjCHO + H20 (36) 

Atf 43 kcal, 

180 kj /mol 

In the industrial process, silver catalysts are preferentially used 

in the form of wire gauzes or crystalline charges. Ethanol vapors 

mixed with air at 3 bar and at 450-550°C are led over the 

catalyst. In accordance with the amount of air a certain temperature ensues at which the heat of oxidation and heat consumption of the dehydrogenation compensate one another. Depending on the reaction temperature there is 30-50% ethanol conversion per pass, the selectivity being 85-95%. The byproducts are acetic acid, formic acid, ethyl acetate, CO, and 

C02. 

In both process modifications, the acetaldehyde is separated 

from the non-reacted alcohol and by-products via various 

washes and distillations and thereby purified. The ethanol recovered from the above is recycled to the reaction. 

to 2: 

oxidative dehydrogenation with process 

characteristics: , 

dehydrogenation as primary step, oxidation 

as secondary step 

most economic operation: 

thermoneutral, i.e. measured amount of air 

brings heat evolution and consumption into 

equilibrium 

both process routes characterized by incomplete ethanol conversion (30-50%) and 

thus by involved distillation and recycle operations 

•its, as 

preanol is 

orCr. 

•ide & 

thanol 

acetal7.3.3. Acetaldehyde via Cj/C4 Alkane Oxidation 

According to a process developed by Celanese and operated in 

the USA since 1943 (capacity in 1969, approx. 160,000 t) 

propane or propane/butane mixtures can be oxidized in the gas 

phase to produce mixtures containing acetaldehyde. The noncatalytic reaction takes place according to a radical mechanism 

at 425-460°C and 7-20 bar. A variant of the Celanese butane 

oxidation process conducted in the liquid phase (cf. Section 

7.4.1.2.) employs oxygen or air as oxidizing agent. Approx. 

15-20% of the hydrocarbon is completely oxidized. The remaining complex reaction mixture contains, besides acetless important acetaldehyde manufacture 

from Cj/C4 alkanes with process characteristics: 

radical, unselective oxidative degradation 

leads to numerous oxidation products 
150 7. Oxidation Products of Ethylene 

involved product .eparation requires considerable investment and operating costs, 

essentially determining the economic 

outcome 

applications of acetaldehyde: 

almost no direct use, but important secondary products such as 

CHjCOOH. (CHjCO).O. 

H2C=C=O.CH,COOC,H,. 

CH3CH=CHCHO n-C4H,0H 

C4H0CH(C,H«|CH,0H. 

etc. 

tendencies in acetaldehyde application: 

increase in AcOH/Ac20 share 

decrease in /i-butanol/2-ethylhexanol share 

<J 

acetaldehyde application dependent on 

country: 

Japan: ethyl acetate 

peracetic acid 

co-oxidation of p-xylene 

W. Germany: ethyl acetate 

aldehyde, mainly formaldehyde, methanol, acetic acid 

M-propanol, methyl ethyl ketone, acetone, and numerous other 

oxidation products. 

The separation of the oxidized products takes place after decomposing the peroxide in an involved, and therefore costly, 

combination of extractions and distillations. 

7.4. Secondary Products of Acetaldehyde 

Acetaldehyde is an important precursor for the manufacture of 

numerous organic heavy chemicals, e.g. acetic acid, acetic 

anhydride, ketene-diketene, ethyl acetate, crotonaldehyde, 

w-butanol, 2-ethylhexanol, pentaerythritol, chloral, pyridines, 

and many others. 

The following table (Table 7-5) relating to the consumption 

breakdown for acetaldehyde shows clearly that the manufacture of acetic acid and its anhydride accounts for the greatest, as 

well as an increasing, share of the acetaldehyde production. 

Furthermore, it can also be seen that the manufacture of 

n-butanol and 2-ethylhexanol, based on acetaldehyde, has become more and more displaced in favor of the propene hydroformylation (cf. Section 6.1). 

Table 7-5. Breakdown of Acetaldehyde Consumption (in wt.-%). 

Acetic acid and anhydride 

•t-Butanol 

2-Ethylhexanol 

Various (e.g. ethyl acetate, 

pyridine, alkylpyridines etc). 

1970 

45 

19 

17 

19 

USA 

1974 

50 

14 

11 

25 

Japan 

1970 1974 

48 58 

18 17 

15 

19 25 

BRD 

1975 

70 

-

-

30 

Acetaldehyde's share of the products listed under "various" 

differs from country to country. For example, in Japan approx. 

14% of the acetaldehyde production was used for ethyl acetate 

(1974) whereas the corresponding W. German figure (1975) 

was as much as 20%. This acetaldehyde application does not 

exist in the USA (cf. Section 7.4.4). In Japan a further 7% was 

employed in 1974 for the manufacture of peracetic acid (cf. 

Section 7.4.1.1) and in the co-oxidation of /••-xylene to 

terephthalic 

areas posse 

Germanv. 

7.4.1. Acet 

Acetic acid 

quantitative 

USA in ll 

country (T 

acid produ' 

Japan the 

recession, 

with almos 

Table 7-6. 

USA 

W. Germai 

Japan 

The prodt 

In some c 

by the fe 

vinegar) t 

is obtaine 

approx. 1 

duced in 

synthetic 

For man\ 

from ace: 

processe: 

Wacker; 

Acetic ac 

facturing 

stock frc 

Moreov* 

drocarbi 

light pa: 

BP.Cel. 

of the C 
P.33 

SH-3*7 

fourth edition 

CHEMICAL 

PROCESS 

INDUSTRIES 

R. NORMS SHREVE 

late Profettor Emeritus of Chemical Engineering 

Purdue L'nivenity 

JOSEPH A. BRINK, JR. 

Consulting Chemical Engineer 

Profettor and Chairman of Chemical Engineering 

Washington State University 

McGRAW-HILL BOOK COMPANY 

.Vw York St. Louil San Franciico Auckland BogoU 

DOlseldorf Johannesburg London Madrid Mexico 

Montreal .Vttr Delhi Panama Pari. Sao Paulo 

Singapore Sydney Tokyo Toronto 

RADIAN LIBRARY 

DURHAM, N.C. 
P.34 

692 [Chap. 38] Petrochemicals 

TABLE 38.4 Petrochemicals from Ethylene in 1974 

Refinerycrocked 

gase 

Produced 

annually, 

millions 

Basic derivatives 

Ethvlene oxide 

Via direct oxidation 

Via chlorohvdrin 

Ethvl alcohol (industrial) 

From ethylene. 96 

By fermentation. 4 

Polvethvlene 

Stvrene 

From ethvlene and ben 

Ethvl chloride 

Ethylene plus hvdrogen 

Qilorination of ethane 

Ethvlene dichloride 

Bv direct chlorination 1 

By-product of ethylene 

Ethylene dibromide 

and sources % 

iene (or reformate} 

chloride 

major) 

chlorohydrin production 

of pounds 

4.260 

2.000 

8.-150 

6.400 

659 

9.300 

325 

Uses, % 

Clvcols, 5 

Glvcol ethers. 7 

Ethanolamines, 6 

Non ionic detergents. 11 

Other. 11 

Aldehvdes. 14 

Other chemicals. 26 

Solvent. 12 

Flavors, cosmetics, detergents. 30 

Other. 18 

Film, sheet, molding, and extrusion. 90 

Polvstvrene, 51 

SBR and latex. 12.5 

Miscellaneous resins. 29.5 

Other. 7 

TEL. -8 0 

Minor amounts for other eth via tions 

(such as ethyl cellulose) 

Vinvl chloride. 78 

Scavenger in antiknock fluid, 3 

Other, 19 

Scavenger in antiknock fluid. 50 

Source: Chem. Mark. Rep. (1974. 1975). 

(cotolyst) 

Polyethylene Ethonolomines 

Ammonia 

Oxygen (catalyst 

Ethylene 

Chlorohydrin 

AlKcli 

Ethylene oxide 

Water 

Hydrogen 

cyanide, 

Chlorine 

Ethylene 

dichloride 

ETHYLENE 

a 

Hydrogen 

chloride 

Dehydrogenation 

Acrylonitrile 

Bromine Ethylene dibromide 

Vinyl chloride 

Cracking 

of ethone, 

propane 

"A \ \ Hydrogen 

\ \ \ chloride 

\ \ Water 

\ (catalyst) 

Sulfuric acid 

Benzene 

Ethyl chloride 

Sulfuric esters 

Ethylbenzene 

Water f 

Ethyl alcohol 

Styrene 

•**•*" Polyglycols 

Ethylene gi >cg l 

Oi-and triethyin 

glycols 

Alcohols or 

alkyl phenols 

Glycol ethers O M ' 

polyglycol ethers 

Fig. 3S.2 Petrochemicals from ethylene. [McGraw-Hill Encyclopedia, vol. 10. p. .6. 1966 (newer plants for acrylonitiik 

stem from propylene): see also Chem. Eng. Dcskbook. 80(23). 34 (1973).| 

(catalyst) 

Fig. 38.3 Petrochemicals from propylene an 

for acrylonitrile 3tem from propylene—see text. 

sumer of butadiene; isobutvlene (rubber). Che' 

Important as these chemical coi 

in the general chapters of this book. • 

ing text. Chemical engineers dire* 

chemical economy have called upon 

to improve their manufacturing in ail 

Indeed, a well-developed chemical pr 

a "system."11 "Svstems," accordir 

1961. 

"White (Atlantic Refining Co.), Chetmca 
P.35 

708 [Chap. 38] Petrochemicals 

k0*dw<,i-r.->y •?•* .3 . 

•>Wrf, i/(i 

PU.S. oxygen capacity production, or 17.000 tons/day in 1976. is consumed in the chemical industry 

Sittig points out that oxygen is often more economical than air. largely because of enhanced yield 

reduced recycle intervals, higher reaction rates, reduced equipment size, and reduced heat loss 

nitrogen. The reactions are carried out in both the liquid and vapor phases, using a variety f 

catalysts. V2 0,. for example. In the latter case, fairly high temperatures (about 400°C) are employ d 

and. since the reactions are highlv exothermic, the problem of heat removal is a large one. Oxidati 

gives synthesis gas (Chap. 71. but hydrogenation converts the CO to methanol, hence the latt 

chemical is presented under Hvdrogenation (q.v.). 

The Celanese Corp.. at its large plants at Bishop and Pampa. Tex., oxidize propane and butan 

as such or as LPG and obtain a large number of oxvgen-containing chemicals. Air has been used but 

in recent enlarged operations, increase in production has resulted from emploving oxvgen. Some of 

the products are methanol, acetic acid, acetic anhvdride. formaldehvde. acetaldehvde. acetone 

butvraidehvde. ethvl acetate, butanol. and vinvl acetate. Partial oxidation is employed to raise the 

temperature and to oxidize partially a hydrocarbon, e.g.. natural gas to make acetvlene (Chap. 7) o r 

under other conditions to furnish channel black (Chap. 8). It is reported that Celanese's new 

acetaldehvde plant at Bav Citv. Tex., involves the largest use of titanium yet reported. 

LPG oxidation takes place with air. Creater production is obtained with oxvgen for anv given 

plant size. Products prepared without a catalvst are acetaldehvde. formaldehyde, methanol, and 

manv oxvgenated petrochemicals. The longer the normal-paraffin chain length and the higher the 

pressure, the easier the oxidation. Catalysts are important and selective: a cobalt catalyst with liquidphase butane vields 76% acetic acid, and 6% formic acid, whereas a manganese catalyst furnishes 

62% acetic and 23% formic acid, this being the experience of Celanese at Pampa.47 Tex., for butane 

liquid-phase oxidation at 800 psig and 175°C. 

Acetaldehyde^ is produced commercially (about 1,600 million lb in 1976) by four methods: 

1. Bv the hydration of acetvlene: 

C,H2 + H20 • CH3CHO 

Yield 95%, conversion 55% 

Acetvlene is passed into a suspension of ferric and mercurous sulfates in sulfuric acid under a pressure of 15 psi between 70 and 100°C (maintained by the heat of reaction). 

2JFrgfl}-eHij!_alcohol. vapor-phased and oxidized to acetaldehvde by passing through a copperor silver-gauze catalvst: 

C.H.OH^) -KW2(£) -*^ » CH3CHO(£) + H20(#) L\H = -4 3 kcal 

Yield 85-95%, conversion 20-35% 

The product is recovered by scrubbing with ethyl alcohol and rectifying to give 99% acetaldehyde. 

."•j Frnifl ethvlene bv the Wacker process developed by Hoechst49 for the direct oxidation of 

ethvlene, using either air or 99% oxygen. The catalyst is an aqueous solution of copper chloride 

(promoter) and palladium chloride, through which ethylene with air or oxygen is passed: 

CH2:CH2 + PdO, + H20 — 

Pd + 2HQ + J02 > Pdd2 

• CH3CHO + Pd + 2HQ 

''Sittig. Combining Oxygen and Hydrocarbons for Profit, chap. 7. pp. 101-I Itl. Fu riptions. rrOr.nrP.. flowcharts. 

and tabulated variations with changes in temperature and pressure on oxygen ratio. 

48Goldstein. op. cit.. p. 332; Sittig. Combining Oxygen and Hydrocarbons fur Profit, pp. 232-234 (flowchart for oxidation 

from alcohol). 

*•"Hydrocarbon Process. S2(ll). 91 (1973). 

The acetaldehyde is vaporized fn 

The acetaldehyde is distilled. T 

depicted in Fig. 38.11. 

4. From lower paraffins, 

produce, among many other com 

is reasonable, only 15 to 20% i 

vielding condensable organic pro 

ucts as pure components requirt 

Acetic acid51 and anhvdn 

Many alternative routes are avai 

The acetaldehyde is oxidizf 

catalyst present to prevent the I 

about 60 psi, and the temperatu 

are separated and purified in a _ 

operating under vacuum. In 19' 

lb of acetic anhydride. The mo 

acetate. It is also employed in v_ 

of acetaldehyde-monoperacetate 

2CH1CHO - 0., 

ultrauol.i Irzhi 

by the controlled low-temperatu 

epoxides or 2 mol of acetic acid 

Ethylene oxide03 is an imp 

ethylene oxide produced being 

wear out, about one-fifth of all et 

hydrin, but an increasing amoc 

ethylene: 

CH., 

ten-fair? • \" 

_..-imp... 

• .t_l, . CH., 

Yield 55-65%, conversion per 

Production in 1974 was 4.26 bi. 

Aromatic oxidation5* prodt. 

indicates, there is a fundament; 

petroleum. See also Fig. 38.4 ai 

OXO- OR HYDROFORMYLA. 

aldehydes and/or alcohols contain 

"Hoechst Reveals Wacker Process. 

42(11). 1963; Cuccioni. Acetaldehvde via 

51Goldstein. op. cit.. p. 373; Sittig. 

Chemicals. Chem. Eng. (.V.K.I. 81(2). 12. 

"Phillips et at.. U.S. Pat. 2.804.473 

^Goldstein, op. cil.. pp. 156-159: h 

••••Phthalic anhvdride flowchart. Fig. ."• 

****Groggins. op. cit.. pp. 651-693 an< 

Oxo Slavs in the Race. Chem. tfeek. June 
976. is consumed in the chemical industry, 

an air. largely because of enhanced yields, 

equipment size, and reduced heat loss to 

uid and vapor phases, using a varietv of 

temperatures (about 400°Q are employed 

n of heat removal is a large one. Oxidation 

is the CO to methanol, hence the latter 

Pampa. Tex., oxidize propane and butane 

itaining chemicals. Air has been used, but 

•esulted from employing oxvgen. Some of 

le. formaldehyde, acetaldehvde. acetone., 

'artial oxidation is emploved to raise the 

atural gas to make acetylene (Chap. 7) or 

8). It is reported that Celanese"s new 

use of titanium vet reported. 

ion is obtained with oxvgen for anv given 

taldehvde. formaldehyde, methanol, and 

•paraffin chain length and the higher the 

ind selective: a cobalt catalyst with liquid-

. whereas a manganese catalvst furnishes 

ol Celanese at Pampa.47 Tex., for butane 

HO million lb in 1976) bv four methods: 

•us sulfates in sulfuric acid under a presheat of reaction), 

''taldehvde bv passing through a copper-

\H * -43 kcal 

nd rectifying to give 99% acetaldehyde-

•>y Hoechst49 for the direct oxidation of 

an aqueous solution of copper chloride 

with air or oxvgen is passed: 

Halogenation and Hydrohalogenation 709 

The acetaldehyde is vaporized from the solution and absorbed in water, separate from residual gases. 

The acetaldehvde is distilled. The conversion and yield are approximately 95%. A flowchart30 is 

depicted in Fig. 38.11. 

4. From lower paraffins. Propane and butane can be oxidized with air noncatalvticallv to 

produce, among manv other compounds, acetaldehvde and acetic acid. The selectivity of the process 

is reasonable, onlv 15 to 20% of the paraffin being oxidized to CO and CO.. and the remainder 

yielding condensable organic products such as acetaldehvde and acetic acid. Recoverv of the products as pure components requires special distillations. 

Acetic acid51 and anhydride using oxygen are produced by the oxidation of acetaldehvde. 

Many alternative routes are available (e.g., fermentation. Chap. 31). 

The acetaldehyde is oxidized by air with methyl acetate diluent and with manganese acetate 

catalyst present to prevent the formation of explosive amounts of peracetic acid. The pressure is 

about 60 psi, and the temperature at 50 to 70°C. The products, acetic anhydride and acetic acid. 

are separated and purified in a series of bubble-cap columns, the crude still and the anhydride still 

operating under vacuum. In 1974, 2,277 million lb of acetic acid were produced and. 570 million 

lb of acetic anhydride. The most important use of acetic anhydride is in the making of cellulose 

acetate. It is also employed in various other acetylations. A development52 has been the production 

of acetaldehyde-monoperacetate (AMP) 

0---H0 H 

2CH3CHO + 02

 u "3t' lif> " . CH 3 3 ^ 

0 0 CH, 

o°c 

by the controlled low-temperature oxidation of acetaldehyde. The AMP can be used to produce 

epoxides or 2 mol of acetic acid. 

Ethylene oxide53 is an important chemical intermediate, yielding ethylene glycol (half of the 

ethylene oxide produced being so consumed), ethanolamines, and acrvlonitrile. Until the plants 

wear out. about one-fifth of all ethvlene oxide is still being made bv the old process through chlorohydrin, but an increasing amount each year is manufactured by air or oxvgen acting on pure 

ethylene: 

C2H4 + |0 2 J___________ 

125-300 ps..' 

calaKst 

CH., 

I \ 

I / 

CH, 

;0</rl _.// = -3 5 kcal 

Yield 55-65%, conversion per pass 25-50%, 

Production in 1974 was 4.26 billion lb. 

Aromatic oxidation54 products are included in various chapters of this book. As Table 37.6 

indicates, there is a fundamental change in the source of aromatics from coal and coal tar to 

petroleum. See also Fig. 38.4 and Table 38.6. 

OXO- OR HYDROFORMYLATION55 The oxo process is a method of converting o-olefins to 

aldehydes and/or alcohols containing one additional carbon atom. The olefin in liquid state is reacted 

'I II - lul l ,l.-., T ,i..n-. r.*>r.n.-.**. fl"«**h*'"-

ratin. 

'- I'T Hn.ni. pp, 232-234 |llu»<*hari for oxidation 

•"Hoechst Reveals Wacker Process. Chem. Eng. \etis. Apr. 17. 1961. p, 52: Petrochemical Handbook: Pet. Rrnner. 

42(11). 1963; Guccioni. Acetaldehyde via Ethylene Oxidation. Chem. Ung. (V. >".). 70(251. 150 (1963i. 

•^Goldstein, op. cit.. p. 373: Sittig. Acetic Acid and Anhvdride. \oves. 1965: Austin. Industrially Significant Organic 

Chemicals. Chem. Eng. (V. )*.). 81(2). 128 (1974). 

"Phillips et ai. U.S. Pat. 2.804.473 (1957). 

"Goldstein, op. cit.. pp. 156-159: Hydrocarbon Process.. 52(11). 129 (1973). 

"Phthalic anhydride flowchart. Fig. 34.12: Hydrocarbon Prore.tt.. 52(11). 159 (1973). 

****Groggins. op. cit.. pp. 651-693 and particularly p. 683 (kinetics and flow diagram): Goldstein, op. cil.. pp. 204ff.: How 

Oxo Stays in the Race. Chem. Week. June 6. 1964: Hahn. op. cit.. pp. 104-116. 
P.37 

710 [Chap. 38] 

in a single stage, 

using oxygen 

Ethylene 

1 

Oxygen 

Petrochemical 

Recycle gas 

s 

Gaseous reaction 

REACTION AND REGENERATION 

mixture 

;d stream 

a_ 

UJ 

S 

o 

h-

!/*> 

i 

•*—water 

Acetaldehyde 

solution 

DISTILLATION 

DEGASSING 

Water 

• Waste gas 

or in two stages, 

using air Reaction mixture with catalyst. 

Offgas 

Ethylene 

Waste air 

1 

S..2 

2 = 

Air 

Crude 

acetaldehyde 

UJ 

a 

Uju. 

QUJ 

Spent catalyst 

acetaldehyde 

• Waste gas 

solution 

Fig. 38.11 Oxidation of ethvlene to acetaldehvde bv the Wacker process. 

Acetaldehyde 

with a mixture of hydrogen and carbon monoxide in the presence of a soluble cobalt catalyst to 

produce the aldehyde (and some alcohol); all or part of the aldehyde is then hydrogenated over a 

nickel catalyst to form alcohol. The reaction is exothermic, about 35 kcal being liberated per grammole of olefin reacted. The usual raw materials are synthesis gas (Chap. 7) and a-olefins. The 

principal olefins used are propylene and the C7 to C12 copolymers of propylene and isobutylene. 

Propylene reacts with synthesis gas to yield the following products: 

CH3CH:CH2 + CO + H2* 

Propylene 

17S*'C. 

250 itm 

CH3CH2CH,CHO + CH3CHCHO + CH3CH2CH,CH2OH + CH3CH2CH,OH 

CH, CH, 

These are, respectively, a-butyraldehyde, isobutyraldehyde, n-butanol, and isobutyl alcohol. 

Industrially most used is the C7 olefin copolymer, which yields the mixture of corresponding 

Cg alcohols. Addition of the CO group to die double bond is about 60% terminal and 40% secondary. 

A typical C7H14 olefin yields the following isoctyl alcohol derivatives: 

3,4-dimethyl-l-he___nol 

3,5-dimethyl-l-hexanol 

4,5-dimeth vl-1 -hexanol 

3-methyl-l-heptanol 

5-methyl-l-heptanol 

Others 

POLYMERIZATION* of pe t 

Industries, Chap. 35, Synthetic 

most important industries are b. 

as presented in Chap. 37. 

MISCELLANEOUS A few 

chemical conversions. Two imt 

former is fully covered in Chap 

Carbon disulfide is now ma 

and sulfur37 is described in CP! 

CH4<*)+ «(,)-*!& - <_-,o, 

'OO'C. 

20-30 p» 

Yield 90% (on methane) per p 

The H2S can be converted 

and cellophane. Production is a 

SELECTED REFEREIVCES 

Augustine, R. l~: Catalytic Hydrogenation. 

Barry. W. R.: Structural Analysis of Petro 

Brownstein. A. M: L.S. Petrochemicals. F 

Edmister. W. C: Applied Hydrocarbon Th 

Gould. R. F. (ed.): Literature of Chemical 

Guthrie. V.: Petroleum Products Handbooi 

Hatch, L F.: Isopropyl Alcohol McGraw-l 

: Higher Oxo Alcohols, Wiley, 195 

Hatton. R. E.: Introduction to Hydraulic E 

Hoiberg, A. J. (ed.): Asphalts, Tars and Pi 

Kobe, K. A., and 1.1. McKetta, Jr. (eds.): 

MeUan, I..* Industrial Solvents Handbook. .' 

: Polyhydric Alcohols, Spartan Boo. 

Sittig, M.: Aromatics. .Moves. 1966 (patent 

: Chemicals from Ethylene. Moves. 

: Chemicals from Propylene. Moves. 

: Pollution Control in the Organic * 

Smith. C W. (ed.): Acrolein. Wiley. 1962. 

Topchiev, A. V., et al.: Synthetic Materials 

Vervalixu C- H.: Fire Protection Manual for 

Waddams. A. L: Chemicals from Petroltun 

"Groggina, op. cit.. pp. 856, 943; Gol< 

'"Sittig, Combining Oxygen and Hydro 

methane process): Haines. Carbon Disulfide. 

38Go__ttein, op. cit., p. 93. reaction cot 
•SimIntroduction to 

Industrial Chemistry 

HOWARD L. WHITE 

CIBA-GEIGY Corporation (Ret) 

A Wiley-lnterscience Publication 

JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • Singapore 
66 

ORGANIC CHEMICAL PROCESSES 

with various catalysts. If this is successful, the process could then be conducted 

at the same throughput temperature as the oxychlorination. 

4.2.3 Acetaldehyde 

A recent review of acetaldehyde (WittcofT, 1983) discusses the latest syntheses 

and uses of this product. We now examine the Wacker reaction, a cyclic process 

for manufacturing acetaldehyde. This process uses an equimolar amount of 

copper(II) chloride and a small quantity of palladium chloride as catalyst. 

PdCI2 + CH 2 =CH 2 + H2 0 - CH3CHO + Pd° + 2HCI (1) 

Pd° + 2CuCI2 - PdCI 2 + 2CuCI (2) 

2CuCI + 2HCI + 0.5O2 - 2CuCI2 + H 2 0 (3) 

Only a catalytic quantity of Pd is needed in this process because the CuCI 2 

reoxidizes the Pd° as soon as it is formed lEq . (2)|. The CuCl formed in the 

oxidation of the Pd is reoxidized to CuCl 2 by 0 2 and HC l |Eq . (3)|. 

A. Mechanism of the Wacker Reaction 

Cl Cf 

.0/ X. 

' ci cr 

ir *-

H2C 

+ C2H< 

U Cl 

H2CS V 

H2C 

Cl 

+ cr 

Cl 

+ H,0^ = Pd + Cl 

H2Cy \ 

H2C 

O H , 

HjC 

II" 

HjC 

3 /* 

Pd 

H2Cy \ 

H,C 

OH 

+ H * 

The rate-determining step is the transformation of the hydroxy ethylene palladium complex into the 0-hydroxy-ethyl palladium complex 

4.2 INDUSTRIAL PROCESSES USING ETHYLENE CHEMISTRY 

[(C2H4)PdCI2(OH)J- + H 2 0 - I(HO-CH 2 -CH 2 )PdCI 2 ( H 2 0)]-

67 

CH 

I 

C H 2 

I 

OH 

ci cr X 

I 

O H 

Cl cf 

\ / 

H3C Pd 

H C ^ S 

I 

O H 

' Cl PI 

H

3C \ f 

H./ V 

-CH,CHO + H * + Pd° + 2 Cl 

S=H 2 0 

FIGURE 4.3 Mechanism of the Wacker reaction. (Reproduced with permission from 

R. Prins, Chemistry and Chemical Engineering of Catalytic Processes, R. Prins and G. 

Schuit, Eds., Copyright 1980 Martinus Nijhoff/Dr. W. Junk, Dordrecht, The Netherlands, p. 423, 425.) 

Figure 4.3 shows the mechanism o f the Wacker reaction. It wil l be discussed 

further in Section 11.2. This mechanism has been discussed by Prins (1980, pp. 

423-425). 

B. Manufacturing Conditions for Acetaldehyde (Wacker Method) 

The process conditions for manufacturing acetaldehyde have been taken from 

the work of Jira et al. (1976, p. 97). See Figure 4.4. 

1. Streams of ethylene and oxygen are separately piped into the bottom o f a 

tower (A) containing copper(II) chloride solution mixed with a small amount 

of palladium chloride. The reactor is held at 130°C and 3 atm pressure. 
ORGANIC CHEMICAL PROCESSES 

68 

Separator 

Light and distillation 

Cooler column 

Scrubber Final distillation 

Off-gas 

Low boiling 

material 

H2OJ 

kondenser ^ 1 Steam, 

fl*-^ i Product 

_ ,, 'it? I I uuuciw.., — cooler 

C2H4 ' 7-± I (10%) I j , 

(99.8%) *>k£ t T 

Gas-cycle pump Crude aldehyde Off-water Product 

FIGURE 4.4 Acetaldehyde manufacturing (low sheet. (Reprinted with permission from 

Hydrocarbon Processing, Vol. 55, no. 3. March, 1976.) 

2. From the reactor (A) is evolved acetaldehyde, water vapor, and unreacted ethylene and oxygen. These gases are sent to the demister-separator (B). Any catalyst solution carried as a mist is returned to (A). 

3. The stream from (B) is cooled in (C) and sent to a scrubber (D). Here 

a water spray dissolves the acetaldehyde forming a solution which is 

carried to vessel (F.). The remaining gases are recycled as shown to (A), 

after any consumed ethylene has been replaced. 

Small amounts of reaction gas arc removed to prevent buildup of contaminants. 

Some of the catalyst solution is sent to the regenerator (H), along with 

sufficient oxygen to convert coppcr(l) to copperdl) chloride and decompose by-products. The temperature in (H) is 170°C. 

6. The erode aqueous acetaldehyde is separated from low boiling material 

in a distillation column (F). which is operated as an extractive distillation 

with water. (Sec Section 9.1.1.) 

7. Acetaldehyde is separated from water in a fractionating distillation column (G). High boiling material is removed as a higher boiling fraction 

or as distillation residue. 

4.2.4 Reactions of Acetaldehyde 

We now review procedures for the manufacture of various products that are 

•o^ri^rt nm on an industrial scale using acetaldehyde as a raw material. 

4. 

5. 

4.2 INDUSTRIAL PROCESSES USING ETHYLENE CHEMISTRY 69 

A. Butanol 

Butanol has been prepared by three processes. The procedures were developed 

because of the need for cost reduction. Only reaction 2 uses acetaldehyde. 

1. Butanol was first prepared by fermentation (see Section 3.1.5), a process 

that may become significant again, depending on petroleum costs. 

2. When petroleum products became inexpensive, the process based on acetaldehyde became popular and was used for many years. This is given in the 

following equation: 

2CH3CHO •*- CH3CHOHCH2CHO - CH3CH = CHCHO 

V' 

CH3CH2GH2GH2OH 

3. The latest process, called hydroformylatton, is discussed in Section 4.3.4. 

To prepare butanol, propylene is the raw material (Wittcoff, 1980). 

C H 3 CH=CH 2 + H2 + CO - CH3CH2CH2CHO 

-» CH3CH2CH2CH2OH + isomer 

Propionaldehyde is the only product of hydroformylatton of ethylene. This is a 

major raw material for propionic acid. 

C H 2 =CH. , + H j + CO - CH3CH2CHO - CH3CH2COOH 

B. Acetic Acid and Peracetic Acid 

This process has been reviewed by Weissermel and Arpe (1978, pp. 152-153). 

Oxidation of acetaldehyde can be made to yield either acetic acid or peracetic 

acid, depending on the conditions. 

CH3CHO - CH3CO ^CH 3 COO O - CH3COOOH 

°

7

 peracetic 

acid 

CH3CHO + CH3COOOH - CH3CHOHOOCOCH3 - 2CH3COOH 

(1) 

(2) 

With mild conditions (15-40°C) at 25 bar and .,r. one gets peracetc ac.a s 

the main product. To make acetic acid, the procedure ,s to acceleratthe ox, 

dation by radical formation as well as decompos e of peraceUc ac £ The 

catalysts used are Mn or Co acetates. The catalyst enters mto the react.on as 

shown: 
AUL-W1 

Shrevc's 

Chemical 

Process 

Industries 

GEORGE T. AUSTIN 

Professor Emeritus of Chemical Engineering 

Washington State University 

Fifth Edition 

McGraw-Hill Book Company 

New York St. Louis San Francisco Auckland Bogota Hamburg 

Johannesburg London Madrid Mexico Montreal New Delhi Panama 

Paris Sao Paulo Singapore Sydney Tokyo Toronto 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK. NC 
P.42 

Manufacture of Petrochemical* 767 

e chloride, 70 percent, and to 

alcohol and ammonia. Methyl, 

nparatively small markets and 

s ammonia in the vapor phase. 

ethod. The problem is to stop 

Usually it is desired to break 

most readily available oxidant 

to carry away much heat and 

a few rare cases, ozone is the 

m air. and the steel industry is 

eral thousand metric tons per 

_lv because of increased yields, 

pment size, and reduced heat 

ised industrially. All oxidation 

lajor problem. The commonest 

impa, Tex., which oxidize provariety of oxygen-containing 

wgen. replacing air. Products 

ivde, formaldehyde, acetone, 

ost of separating such mixtures 

lection for LPG oxidation gives 

1-phase oxidation of butane at 

.•etic acid and 6 percent formic 

etic and 23 percent formic. 

; oxidation. The major process. 

> ed bv decomposition to phenol 

nl is also made by the oxidation 

sition of hydrocarbons. Examples are the manufacture of carbon black (Chap. 8) and acetylene (Chap. 7). 

In Europe, formic acid is made by the oxidation of formamide. "All formic acid produced 

in the United States is produced as a by-product of the liquid phase oxidation of n-butane to 

acetic acid."27 The by-product source is expected to dry up in the future, and the most promising route to replace it is through carbonylation of methanol. 

Caprolactam, adipic acid, and hexamethylene diamine1* are all made from cyclohexane. 

Almost all high-purity cyclohexane is obtained by hydrogenating benzene, although some for 

solvent use is obtained by careful distillation of selected petroleum fractions. 

Several oxidative routes are available to change cyclohexane to cyclohexanone, cyclohexanol, and ultimately to adipic acid or caprolactam. If phenol is hydrogenated, cyclohexanone 

can be obtained directly; this will react with hydroxylamine to give cyclohexanone oxime 

which converts to caprolactam on acid rearrangement (Chap. 35). Cyclohexane can also be 

converted to adipic acid, then adiponitrile, which can be converted to hexamethylenediamine. Adipic acid and hexamethylenediamine are used to form nylon 6,6. This route to 

HMDA is competitive with alternative routes through butene. 

Acetaldehyde has a brisk sale as a precursor of acetic acid, 1,3-butylene glycol, glyoxal, 

pentaerythritol, peracetic acid, and pyridines. The demand in 1981 was 409 X IO6 kg. There 

are several competing processes. (1) The older process by the hydration of acetylene is no 

longer significant. (2) The Wacker process developed by Hoechst29 starts with ethylene and 

oxidizes it directly with air or 99% oxygen (Fig. 38.9). The catalyst is palladium chloride with 

a copper chloride promoter. The ethylene gas is bubbled, at atmospheric pressure, through 

the solution at its boiling point. The heat of reaction is removed by boiling of the water. 

Unreacted gas is recycled following condensation of the aldehyde and water, which are then 

separated by distillation. (3) Passing ethyl alcohol over a copper or silver gauze catalyst gives 

27Aquilo and Horlenko, Formic Acid, Hydrocarbon Process. 59 (11) 120 (1980). 

MLowenheim and Moran, op. cit., p. 201. 

"Acetaldehyde, Hydrocarbon Process. 60 (11) 121 (1981). 

ear. Most v54 percent) goes into 

-.• plasticizers. benzoyl chloride, 

liquid-phase toluene oxidation 

•nt. An older process25 involving 

•sition into benzoic acid is still 

if the oxidation of xylenes and 

allv by the partial oxidation of 

tion. and several modifications 

c starting materials, 

hus bring about the decompo-

.1981) 

-,-s. Hydrocarbon Proeeas. 39 *6) 

Products and steam 

Reactor 

contains catalyst 

in solution 

Water 

Ethylene| 

Air 

X 

Preliminary 

oxidizer 

Waste 

gases 

Condenser -l 

Aldehyde 

still 

Steom 

Waste 

gases 

1 ' Condenser 1 s Condense t r 

Acetaldenyde 

Purification still 

Crotonaldehyde 

Ok 

CJ) Reboiler 

Spent catalyst solution 

High boilerFig. 38.9. Flowchart for acetaldehyde by air oxidation of ethylene. 
768 Chap, a* Petrochemicals 

about a 25 percent conversion to acetaldehyde, with recirculation making a 90 to 95 

yield possible. (4) Lower molecular weight paraffin hydrocarbons are oxidized no

 PCr?*n

* 

cally to produce mixed compounds, among them acetaldehyde and acetic acid Se ' 

such mixtures is difficult. ' parat,0»of 

Since nearly 50 percent of the acetaldehyde produced is used to make acetic acid its f 

market is questionable. Acetic acid produced directly by the carbonylation of methanol* h" 

already cut deeply into the market. *•* 

Acetic acid is widely used, and much is converted to acetic anhydride.31 

Eastman32 is currently building a very large plant to produce these and other chem 

from coal. The reaction between ketene and acetic acid produces the anhydride b t'k 

amount of energy required to produce the ketene (acetone is cracked to eive 3.. . ! 

... . ,

 & ^ciene and methane) is very large. 

i i-l 

(CH3)2CO - CH2 = C = 0 + CH< 

C H 2 =C= 0 + CH3COOH — (CH3CO)20 

Ketene is used immediately after manufacture because it does not store well. The major •__. 

of acetic anhydride is in making vinyl acetate and other acetylations. 

Ethylene glycol,33 used in antifreeze, 40 percent, and in fibers and films, 50 percent is a 

major petrochemical and has been for many years. The demand in 1981 was 2 X 109 ke 

Like most of the other alcohols, it was originally made by reacting chlorine and water (HOCI) 

with ethylene to form the chlorohydrin, which was then hydrolyzed to yield glycol. This 

procedure and several others (formaldehyde + C02, fermentation, oxidation of propane) is 

now technically and environmentally obsolete. The currently favored process starts with ethylene and reacts it with oxygen or air in a tubular reactor over a silver oxide catalyst to t-*rm 

ethylene oxide. Because the volatility of glycol is low, it is preferable to purify the ethvlene 

oxide, then convert it to glycol by hydration. During the hydration, however, polyglyiols, 

particularly di- and tri-ethyleneglycols are formed. The reactions are: 

HrtC'^'^CHo 1/2 0, 

A«,0 

CH,—CH, + (CO, and H,0 by combustion) 

0 

CH,—CH, •*• H,0 • 

\ / 

CH2—CH2 + polyglycols 

OH OH 

Ethylene dichloride (under 1 ppm) is added to a mix of ethylene and air in the ratio of 1:10 

to reduce oxidation to COj, and the mixture is passed over a supported silver oxide catalyst 

at atmospheric pressure and 280°C with a 1-s contact time. This causes a 60 to 70 percent 

'"Roth et al., Low Pressure Process for Acetic Acid via Carbonylation of Methanol, CHEMTECH 1(10) 600 (1971). 

31

 Jeffreys, The Manufacture of Acetic Anydride, 2d ed., The Institution of Chemical Engineers, London, 1964. 

32

 A Giant Step: Acetic Anhydride from Coal, Chem. Week 127 (3) 40 (1980). 

^Hydrocarbon Process. 60 (11) 161-163 (1981). 

•41 3 ••!•• 
Riegel's 

Handbook of 

Industrial Chemistry 

EIGHTH EDITION 

Edited by 

James A. Kent 

Detroit, Michigan 

TORONTO LONDON MELBOURNE 
H*.\^cV* 1 •VK 

938 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY 

Fig. 25.11 Vapor-phase direct hydration of ethylene to ethanol. {Hydrocarbon Processing, 50, no. 11, ISI 

(1971); copyright 1971 by Gulf Publishing Co.) 

Ethylbenzene 

Ethylbenzene has but one major end-use and 

that is the manufacture of styrene. In 1978, 

ethylbenzene was the fifth largest consumer of 

ethylene, accounting for about 2.26 billion 

pounds.* This represents about a 7 percent 

average annual growth in the last ten years. 

In addition to being produced by the alkylation of benzene with ethylene, ethylbenzene 

is also isolated from mixed xylene streams or 

as a by-product of cumene manufacture. These 

latter sources account for less than 10 percent 

of the ethylbenzene used today. 

Ethylbenzene synthesis by reaction of ethylene with benzene is carried out either in the 

liquid phase using aluminum chloride as the 

catalyst, or in the vapor phase with a phosphoric acid or alumina-silica catalyst. Yields 

about 95 percent are obtained in either case. 

Figure 25.12 shows a flow diagram of an ethylbenzene process. 

The principal uses for styrene, made by 

catalytic cracking of ethylbenzene, are in 

polystyrene, styrene-butadiene latex and plastics, SBR rubber, and in the cross-linking of 

unsaturated polyester resins, 

see Chapter 10. 

For more details, 

Acetaldehyde, Acetic Acid, Vinyl Acetate 

Acetaldehyde. Acetaldehyde production peaked 

in 1969 at 1.65 billion pounds. Of this, 685 

million or 42 percent was made by direct 

oxidation of ethylene. In 1978, production 

was one billion pounds. Over 97 percent of 

this was by ethylene oxidatiofiri The direct 

oxidation process uses cupric chloride and a 

small amount of palladium chloride in aqueous 

jsMottgnas the catalyst. The reaction is exo--

thermic and is controlled by evaporation. The 

gaseous reaction mixture is scrubbed to remove 

acetaldehyde and overhead gases are recycled. 

The liquid from the reaction mixture is regenerated with oxygen to return the copper to 

the cupric state and palladium metal back to 

palladium chloride. See Figure 25.13. 

The alternate processes consist of oxidation 

of ethyl alcohol and glycerin by-product. 

About 70 percent of acetaldehyde consumed 

is used for the production of acetic acid and 
SYNTHETIC ORGANIC CHEMICALS 937 

>0, no. 11. 151 

more details, 

Acetate 

uction peaked 

Of this, 685 

le by direct 

, production 

7 percent of 

The direct 

loride and a 

le in aqueous 

action is exo-

-oration. The 

bed to remove 

are recycled. 

nixture is rethe copper to 

netal back to 

.13. 

of oxidation 

roduct. 

/de consumed 

:etic acid and 

<=? 

Monoalkylated 

Product 

Recycle Benzene 

Recycle Paly alkyl Benzenes 

Fig. 25.12 Alkar ethylbenzene procett. {Hydrocarbon Proceuing, SO, no. 11, 125 {1971): copyright 1971 by 

Gulf Publishing Co.) 

anhydride. Pentaerythritol, peracetic acid, 

pyridine, glyoxal, 1,3-butylene glycol, and 

chloral all combined consume the remaining 

30 percent of acetaldehyde. Since the fate of 

acetaldehyde is determined by its use as an 

acetic acid-acetic anhydride intermediate and 

future acetic acid technology appears to be 

firmly based on methanol, acetaldehyde consumption will drop over the next few years. 

High unit-value products are derived from 

pyridine compounds; thus, although mass consumption of acetaldehyde will not look exciting, growth in value of products will be 

attractive. 

Separator 

Reaction Gase* 

Reactor 

Acetaldehyde 

Fractionator 

Water 

Air Steam 

Water 

Acetaldehyde 

Catalyst 

Regeneration 

Section 

Stripper 

-Steam 

e_3-

Recycle 

Compressor 

Water and 

Heavy 

Impurities 

Fig. 26.13 Acetaldehyde by tingle-ttage Wacker procan. {Hahn, A. V., "Tha Petrochemical Industry,"p. 243, 

McGraw-Hill, 1970.) 
P.47 

S T ~ ^ o

r ^ 

198 9 DIRECTORY OF 

CHEMICAL PRODUCERS 

UNITED STATES OF AMERICA 

Information in this Directory is for the sole 

and private use of sponsors of the 

Directory of Chemical Producers Program. 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK, NC 
P.48 

PRODUCTS 

1989 DIRECTORY OF CHEMICAL PRODUCERS 

UNITED STATES 

Abboticine (See: Erythromycin stearate under Medicinal 

(Pharmaceutical) Chemicals) 

Abomasal enzyme (See: Rennin under Enzymes) 

ABS resins (See,: Acrylonitrile-butadiene-styrene resins under 

Plastics and Resins) 

6-ACA (See: 6-Aminocephalosporanic acid under Medicinal 

(Pharmaceutical) Chemicals) 

Accelerators (See: Rubber Processing Chemicals) 

Acclaim® 1EC (See: Fenoxaprop-ethyl under Pesticides) 

Acephate (See: Pesticides) 

Acetal (See: Flavor and Fragrance Chemicals) 

Acetaldehyde (Acetic aldehyde) (Ethanal) (Ethyl aldehyde) 

Eastman Kodak Company 

Eastman Chemical Products, Inc. 

Texas Eastman Company 

Hoechst Celanese Corp. 

Hoechst Celanese Chemical Group, 

Inc. 

Longview, Texas 

Bay City, Texas 

Annual Capacity 

(Millions of Pounds) 

500 

250 

Raw Material 

Ethylene 

Ethylene 

TOTAL 760 

Note: Hoechst Ceianese's 450 million pound-per-year plant at Clear Lake, Texas, has been idle since 1981, and probably will not be restarted. 

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

Acetaldehyde, diethyl acetal (See: Acetal under Flavor and 

Fragrance Chemicals) 

Acetaldehyde 1,1-dimethylhydrazone 

Dixie Chemical Company Bayport, Texas 

Acetaldehyde, diphenethyl acetai (See: Phenethyl acetal 

under Flavor and Fragrance Chemicals) 

Acetaldehyde, dipropyl acetal (See: 1,1-Dipropoxyethane 

under Flavor and Fragrance Chemicals) 

Acetaldehyde ethyl cis 3-hexenyl acetal (See: Leaf acetal 

under Flavor and Fragrance Chemicals) 

Acetal resins (See: Polyacetal resins under Plastics and Resins) 

Acetamide (Acetic acid amide) 

Henley Manufacturing Inc. 

General Chemical Corporation 

Whittaker Corporation 

Chemicals Group 

Heico Division 

Acetamidoadamanthane 

E. I. du Pont de Nemours & Company, 

Claymont, Delaware 

Delaware Water Gap, 

Pennsylvania 

Agnchemicals Department Linden, New Jersey 

1-Acetamido—4-aminobenzene (See: 4'-Aminoacetanilide) 

p-Acetamidoaniline (See: 4'-Aminoacetanilide) 

2-Acetamidoethanol (See*. N-[2-Hydroxyethyl] acetamide) 

4-Acetamido-2-ethoxybenzoic acid, methyl ester (See: 

Ethopabate under Medicinal (Pharmaceutical) Chemicals) 

4-Acetamidophenol (See: Acetaminophen under Medicinal 

(Pharmaceutical) Chemicals) 

Acetamidothymol 

Hercules Incorporated 

Resins, division 

Reichhold Chemicals, Inc. 

Coating Polymers & Resins Division 

Jefferson, Pennsylvania 

Gulfport, Mississippi 

5-Acetamido-2,4,6-triiodo-N-methylisophthalamic acid 

(See: lothalamic acid under Medicinal (Pharmaceutical) Chemicals) 

Acetaminophen (See: Medicinal (Pharmaceutical) Chemicals) 

Acetanilide (Acetylaminobenzene) (Acetylaniline) (NPhenylacetamide) 

Merck & Co., Inc. 

Merck Chemical Manufacturing 

Division Albany, Georgia 

Acetanisole (See: 4'-Methoxyacetophenone under Flavor and 

Fragrance Chemicals) 

Acetate C-9 (See: Nonyl acetate under Flavor and Fragrance 

Chemicals) 

Aceteugenol (See: Eugenyl acetate under Flavor and Fragrance 

Chemicals) 

Acetic acid (Ethanoic acid) (Methanecarboxylic acid) (See also: 

Peracetic acid) 

Borden Chemicals and Plastics 

Partnership Geismar, Louisiana 

Eastman Kodak Company 

Eastman Chemical Products, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Annual Capacity 

(Millions of Pounds) 

140 

160 

350 

Process and Remarks 

Methanol carbonylation; plant 

restarted with approximately 40 

million pounds of capacity in 

January 1988; remaining 

capacity is on standby. 

Coal qas coproduct 

Acetaldehyde oxidation 

SRI International 

(Continued) 

427 
P.49 

K£-M-MO 

KIRK-OTHMER 

CONCISE ENCYCLOPEDIA 

OF CHEMICAL TECHNOLOGY 

PLEASE DO NOT 

REMOVE FROM 

LIBRARY 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK, NC A WIIEY-INTERSCIENCEPUBLICATION 

John Wiley & Sons 

NEW YORK • CHICHESTER - BRISBANE - TORONTO • SINGAPORE 
P.50 

'•\-rtrnt. (<iVfc. -QtPii/r. ±r b/xcucOo m$ ACETALDEHYDE 

plates can be computed analytically using a special form of the Kremser 

equations. 

CR. WILKE 

URS VON STOCKAR 

University of California, Berkeley 

T.K. Sherwood, R.L. Pigford, and CR. Wilke, Mass Transfer, McGraw-Hill 

Book Co., Inc., New York, 1975. 

R.E. Treybal, Mass Transfer Operations. McGraw-Hill Book Co., Inc., New 

York, 1955. 

CR. Wilke and U.V. Stockar, Ind. Eng. Chem. Fundam. 18<2), 88 (1977). 

R.H. Perry and CH. Chilton, eds.. Chemical Engineer's Handbook, 6th ed., 

McGraw-Hill, Inc., New York, 1983. 

ACACIA. See Diuretics; Gums and mucilages. 

ACAROID, ACCROIDES. See Resins, natural. 

A€tTAtDtKYDE 

Acetaldehyde, CH3CHO, is a colorless, mobile liquid with a pungent 

odor that is somewhat fruity and pleasant in dilute concentrations. It is 

an important intermediate in the production of acetic acid, acetic 

anhytjride. ethvl acetate, peracetic acid, pentaerythritol. chloral, glyoxal. 

alkvlamines. and pyridines, and was used extensively during World War 

I as an intermediate for making acetone from acetic acid. 

Acetaldehyde occurs in traces in all ripe fruits that have a tart taste 

before ripening; it is an intermediate product of alcoholic fermentation 

but is reduced almost immediately to ethanol (see Fermentation). An 

intermediate product in the decomposition of sugars in the body, it 

occurs in traces in the blood. Acetaldehyde is a product of most hydrocarbon oxidations. 

Physical Properties 

Acetaldehyde is miscible in all proportions with water, and most 

organic solvents such as acetone, benzene, ethyl alcohol, ethyl ether, 

gasoline, paraldehyde, toluene, xylenes, turpentine, and acetic acid. 

Table 1 gives some of the physical properties of acetaldehyde. 

Chemical Reactions ( a-cs^-^lrlaJ^-rle. —^- . ) 

Acetaldehyde is a highly reactive compound exhibiting the 

reactions of aldehydes (qv). Acetaldehyde decomposes at tempej 

above 400°C to form methane and carbon monoxide. In aqueous soluTablel. Physical Properties of Acetaldehyde 

Properties Values 

melting point 

boiling point at 101.3 kPa (1 atm), "C 

density, g/cm*1 

refractive index, nTM 

vapor density (air - 1) 

specific heat at 0°C, J/(g- K)a 

at 25°C 

latent heat of vaporization, kJ/mol" 

heat of solution in water at 0°C, kJ/mol" 

at 25°C 

flash point, closed cup, °C 

ignition temperature in air, °C 

explosive limits of mixtures with air, vol % 

acetaldehyde 

"To convert J to cal, divide by 4.184. 

-123.5 

20.16 

0.8045 

1.33113 

1.52 

2.18 

1.41 

25.71 

-8.20 

-6.82 

-38 

165 

4.5-60.5 

tions, it exists in equilibrium with the hydrate, CH3CH(OH)2. The enol 

form, vinyl alcohol (CH2=CH0H), exists in equilibrium with acetaldehyde to the extent of approximately one molecule per 30,000. Acetaldehyde enol has been acetylated with ketene to form vinyl acetate. 

Depending on the reaction conditions, it is readily oxidized with 

oxygen or air to form acetic acid, acetic anhydride, and peracetic acid 

(see Acetic acid and derivatives). Peracetic acid is formed commercially, 

either through low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or ozone; or directly by 

liquid-phase oxidation with a cobalt salt catalyst (see Peroxides and 

peroxy compounds). The nitric acid oxidation of acetaldehyde yields 

glyoxal. 

Acetaldehyde is readily reduced to ethanol (qv), using catalysts such 

as nickel and copper oxide to support the vapor-phase hydrogenation. 

When a mineral acid, such as sulfuric, phosphoric, or hydrochloric acid, 

is added to it, paraldehyde, 2,4,6-trioxane, a cyclic trimer, is formed. 

Metaldehyde, a cyclic tetramer, is formed at temperatures below 0°C in 

the presence of dry hydrogen chloride or pyridine-hydrogen bromide. 

Polyacetaldehyde, an unstable, rubbery polymer with an acetal structure, forms in a few days from acetaldehyde; polyacetaldehyde has no 

practical significance (see Acetal resins). 

The base-catalyzed condensation of acetaldehyde leads to the dimer 

acetaldol, which can be hydrogenated to form 1,3-butandiol, or dehydrated to form crotonaldehyde, which may also be made directly by the 

vapor-phase condensation of acetaldehyde over a catalyst. The basecatalyzed reaction of acetaldehyde with excess formaldehyde is the 

commercial route to pentaerythritol (see Alcohols, polyhydric). The 

vapor-phase reaction of acetaldehyde and formaldehyde at 475°C over a 

catalyst gives acrolein. Ethyl acetate is commercially produced by the 

Tischenko condensation of acetaldehyde with an aluminum ethoxide 

catalyst; with isobutyraldehyde, this yields a mixture of ethyl acetate, 

isobutyl acetate, and isobutyl isobutyrate. Butadiene (qv) can be made 

by the reaction of acetaldehyde and ethyl alcohol. The Strecker amino 

acid synthesis gives alanine (see Amino acids). Grignard reagents give 

secondary alcohols. 

Manufacture ( ***«H0*~*t» *****k*^^: fr**& 

v

 lTM*.(>*Kr>t& 

Acetaldehyde is produced commercially by the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, partial oxidation 

of hydrocarbons, and the direct oxidation of ethylene.

 Th ° AireSt IJT"'*-

phase oxidation of ethvlene (the Wack^-l-fnprhst nrn^pj-s) js thp nrr***.**.. 

of choige: in 1976, 29 companies with > 82% of the world's 2.3 x IO6 

t per year plant capacity used this process. A catalytic solution of 

lalladium chloride is used to form acetaldehyde: 

C H2=CH2 + PdCl2 + H2 0 - CH3CHO + Pd + 2 HCl 

The metallic palladium is reoxidized to PdCl2 with CuCl2, and the 

cuprous chloride formed is reoxidized with oxygen or air. The net result 

is a process in which ethylene is oxidized continuously through a series of 

oxidation-reduction reactions. 

There are two variations for the production of acetaldehyde by the 

oxidation of ethylene: the two-stage process developed by Wacker-Chemie 

and the one-stage process developed by Farbwerke Hoechst. In the 

two-staee process, ethylene and oxygen (air) react in the liquid phase in 

two stages. In the first, the ethvlene is almost completely converted to 

acetaldehyde in one pass in a tubular plug-flow reactor made of titanium. 

Acetaldehyde produced in the first reactor is removed bv adiabatic 

flashing in a tower. The catalyst solution is recycled from the flash-tower 

base to the second stage, or oxidation, reactor, where the cuprous salt is 

oxidized to the cupric state with air. Intjw^fljkgtaggjjrocess, ethylene, 

oxygen, and recycled gas are directed to a vertical reactor for contact 

with the catalvst solution. 

Acetaldehyde is produced commercially by the catalytic oxidation of 

ethyl alcohol, carried out by passing alcohol vapors and preheated air 

over a silver catalyst at 480°C. Older commercial processes produced 

acetaldehyde by the hydration of acetylene under pressure in a vertical 

reactor containing a mercury catalyst dissolved in sulfuric acid. 

Acetaldehyde may also be made from methyl vinyl ether and ethylidene 

diacetate, both of which can be made from acetylene. It is also formed as 

\ 
ACETAL RESINS 

P.51 

a coproduct in the vapor-phase oxidation of saturated hydrocarbons, eg, 

butane or mixtures containing butane, with air, or, in higher yield, 

oxygen (see Hydrocarbon oxidation). Unlike the acetylene route, this 

method has almost no chance to be used as a main process. 4££tAldfi_tt__e 

is produced in a rhodium-catalvzed-orgrey* <**«p«hlg of wiwcrtinf ayfl-'-T*'-

sis gas (^U + H2) directly into acetaldehvde in a sineie_step. IJ\ the 

ypflrs l^w.*. _n[| hevonrij interna. In t^c ••-_» of synthesis gas from coal 

jT_c^,-„_i_,r, pt; a raw material for acetaldehyde production will increase 

(see Fuels, synthetic). ^—•—•**• » 

Health and Safety Factors 

Although in normal industrial operation there is no health hazard in 

handling acetaldehyde if normal precautions are taken, it may be harmful in the following ways: it paralyzes the respiratory muscles, causes 

panic, has a general narcotic action which prevents coughing, causes 

irritation of the eyes and mucus membranes, accelerates heart action, 

and causes headache and sore throat when breathed in high concentrations. Carbon dioxide solutions in acetaldehyde have a weakened odor 

and are particularly pernicious. Prolonged exposure causes a decrease in 

red and white blood cells and a sustained rise in blood pressure. The 

maximum allowable concentration of acetaldehyde in air is 200 ppm. 

Mixtures of acetaldehyde vapor with air are flammable and explosive if 

the concentrations of aldehyde and oxygen rise above 4 and 9%, respectively. 

Economic Aspects and Uses 

Future growth will depend on the development of a lower cost process 

based on synthesis gas, and an increased demand for processes based on 

acetaldehyde activation techniques and peracetic acid. Since 1940, the 

production pattern has changed from hydration of acetylene and oxidation of ethyl alcohol to liquid-phase oxidation of ethylene using the 

Wacker-Hoechst processes. Acetaldehyde production is linked with the 

demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate 

resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, 

terephthalic acid, and peracetic acid. No new acetaldehyde-based plants 

are expected due to the rising costs of ethylene aa feedstock costs 

increase. Methanol carbonylation is the preferred route to acetic acid 

and will continue for the next 10-15 years (see Acetic acid). 

H.J. HAOEMAYER 

Texas Eastman Company 

R. Jira and W. Freiesleben, "Olefin Oxidation and Related Reactions with 

Group VIII. Noble Metal Salts," in E. Becker and M. TsutsUi, eds., 

Organometallic Reactions, Vol. 3, Interscience Publishers, a division of John 

Wiley & Sons, Inc., New York, 1972. 

J. Smidt and co-workers, Angew. Chem. 71, 176 (1959). 

U.S. Pat. 3,240,803 (Mar. 15, 1966), B. Thompson and S.D. Neeley (to 

Eastman Kodak Co.). 

U.S. Pat. 3,714,236 (Jan. 30, 1973), H_N. Wright and HJ. Hagemayer, Jr. (to 

Eastman Kodak Co.). 

ACETAL RESINS 

Acetal resins, also known as polyoxymethylenes, polyacetals, and 

aldehyde resins, are engineering thermoplastics that have broad use as 

replacements for metals in a wide variety of applications (see Engineering plastics). They are high molecular weight polymers with a basic 

molecular structure of repeating carbon-oxygen links. 

^CH,. .CH... CH. XH, CH,. m . 

' ^o o o N>^ ^ 

This alternating oxymethylene structure, OCH2, gives the resins a 

chemistry similar to the simple acetals. Homopolymers consist solely of 

this carbon-oxygen backbone, whereas copolymers have the oxymethylene structure occasionally interrupted by a comonomer unit such as an 

ethylene linkage from ethylene oxide. 

Properties vary depending on the number-average molecular weight, 

the type of additives or reinforcing agents, and whether the resin is a 

copolymer or a homopolymer. For example, additives, eg, glass fibers in 

the copolymer, can improve tensile strength and stiffness (see Composites; Laminated and reinforced plastics). The resins possess high 

stiffness, excellent dimensional stability, high tensile and impact strength, 

good abrasion resistance, and a low coefficient of friction. They resist 

attack by many organic compounds, but are unsuitable in contact with 

strong acids. The copolymer offers superior resistance to strong bases. 

Acetal resins are covered by Federal Specifications L-P-392a and by 

ASTM Specification D 2133 which identify the resin by specific gravity, 

melting point, and melt flow rate. 

Acetal resins are frequently used to reduce cost and improve performance in applications where one acetal part replaces several metal parts, 

(see Engineering plastics). 

Trade names and producers of commercial products include Delrin 

(DuPont), Celcon (Celanese), Hostaform (Celanese—Hoechst), Duraon 

(Celanese—Diacel), and Ultraform (BASF-Degussa). 

Manufacture 

Homopolymer. Commercial homopolymer production is based on the 

polymerization of formaldehyde through monomer purification, poly- , 

merization, end-capping with alkyl or acyl groups, and finishing. The 

concentration of chain-transfer agents must be reduced, although high 

molecular weight polymers have been produced with as much as 0.9*. 

water present. The monomer is purified through scrubbing with an inert 

liquid, partial polymerization to remove chain-transfer impurities, conversion of formaldehyde to a hemiformal and subsequent decomposition 

to purified formaldehyde, and treatment with P205. 

There are two main polymerization reactions: the first is addition to 

the double bond of the monomer. The second is growth of a completely 

crystalline polymer in aqueous or alcohol medium by stepwise equilibrium with solvated monomer using crystallization as the driving force. 

Anionic initiators include amines, phosphines, ammonium and sulfonium 

salts, amides, amidines, etc. 

-CH2 0 " + CH2=0 - ~CH2OCH20" (anionic) 

-OCHJ+ 0=CH2 - -OCHjOCHj* (cationic) 

Cationic initiators include sulfuric or phosphoric acid, Lewis acids, and 

stable cations. Ionizing radiation is also effective. The polymer is endcapped for stabilization by reaction with acetic anhydride. It is finished 

with the addition of antioxidants, typically of the amide or amine type. 

Copolymer. Commercial copolymers are made by the trimerization 

of formaldehyde to trioxane, purification of trioxane, copolymerization, 

stabilization by alkaline hydrolysis, and finishing. The copolymerization 

of trioxane, like formaldehyde polymerization, is by cationic initiation 

using, in this case, boron fluoride etherate or other boron fluoride 

coordination complexes with organic compounds. Cationic polymerization is relatively complicated and may involve the oxonium ion as well as 

the carbocation. Tranaacetalization can. occur as a side reaction. The 

polymerization is carried out in the presence of 0.1-15 mol% of the 

comonomer, yielding a polymer having 85-99.9$ oxymethylene units 

(—OCH2—); thus, the polymer is still predominantly a polyoxymethylene, allowing its classification as an acetal resin. 

Health and Safety Factors 

During the processing of acetal resins in molding or extrusion equipment, some decomposition can occur with evolution of formaldehyde. 

Formaldehyde, as an air contaminant, is regulated under OSHA. The 

National Sanitation Foundation has listed a number of acetal compositions for use in contact with potable water. The FDA regulations 21 

CFR 177.2470 and 21 CFR 177.2450 cover acetals repeatedly used in 

contact with food. 

K J. PERSAK 

L.M. BLAIR 

E.I. du Pont de Nemours & Co., Inc. 
P.52 

common Synonyme 

Acetic aldehyda 

Ethintl 

Ethyt aldehyde 

Floats tnd mix*, mtfi water. 

Bo*ng point n 69'F. 

Sharp, fruity odor 

Flammable, irritating vapor is produced 

Avoid contact witn iiquia and vapor Keeo people away. 

Wear goggles and seit-contained breaming apoaralus. 

Shut oft ignition sources ano call 'ire department, 

Slay upwind ano use water spray to knock down" vapor. 

Stop discharge if possible. 

'scale ano remove aiscnarged material 

Notify local neaitn and pollution control agencies 

Fire 

Exposure 

Water 

Pollution 

FLAMMABLE. 

Flashback along vapor trail may occur. 

Vapor may explode rf ignited in an enclosed area. 

wear goggies and seil-contained Dreathtng apparatus. 

Combat tires irom safe distance or protected location 

Extinguish with dry chemical, alcohol foam, or cartoon dioxide 

Water may t» ineffective on tire. 

Cooi exposed containers with water 

CALL FOR MEDICAL AID 

VAPOR 

irritating to eyes, nose and throat 

If inhaled, will causa nausea, vomiting, headache, difficult breathing, 

or loss of consciousness. 

Move to fresn air. 

11 breathing has stooped, give artificial respiration, 

if breathing is difficult, give oxygen. 

LIQUID 

WW bum skin and eyas. 

Harmful if swallowed. 

Remove contaminated clothing and shoes. 

Flush affected areas with plenty of water. 

IF >N EYES, hotd eyelids open and flush with plenty of water. 

IF SWALLOWED and victim is CONSCIOUS, have victim dnnh water 

or milk. 

HARMFUL TO AQUATIC UFE IN VERY LOW CONCENTRATIONS. 

May ba dangerous it it enters water intakes. 

Notify local health and wildlife officials. 

Notify operators of nearoy water intakes. 

1. RESPONSE TO DISCHARGE 

{800 Roeponoo Methods HamWwofc) 

Isauo warning-high flanvnabiMy 

Disperse and (lush 

3. CHEMICAL DESIGNATIONS 

3.1 CO Compa_b4_ty Ctaaas Aldehyde 

3.2 Formula: CHiCHO 

3J IMO/UN Designation: 11/1089 

1.4 DOT ID No- 1009 

3.9 CAS Reglatry No.* 7S-07-0 

2.1 

U 

I LABEL 

0-_a:3 

4. OBSERVABLE CHARACTERISTICS 

4.1 Physical State (aa shipped* Liquid 

4J Color Colorless 

4 J Odor Pono-abng, maty, inarp pungent 

S. HEALTH HAZARDS 

9.1 Paraonal Proloc-vo Equipment Rubber gloves, ay* goggles, and otnar equipment 10 pravant 

any contact with body. &ganic canistar or ar pack aa required. 

Jm\ Symptomo . oBoartng Expooura: Breathing vapora wil bo irritating and may cauaa nauiaa. 

vomiting, headache, and unoonodouanaaa. Contact with ayoa may cauaa bums. Skin contact 

Irom clothing wai wKti mechanical rauaai buma or aavaro rrttation. 

5.3 Troatmant of Expooura: INHALATION: ramova victim to Iroah _r il breelhing Itaa stopped, givo 

artilicual reapraoon* il biaatliing ia difficult, giva oxygon; cal a phyaician at onco. SKIN: wash 

with aoap and watar. EYES: fluah wan watar. 

9.4 ThraanoM umtt latum 100 ppm 

9.9 Short Tam limalamm Umtta: 50 ppm Mr to nan 

5.4 Toxicity by Ingestion. Grado 2; LO.o • 0.9 to Sg/kg (rs« 

5.7 Lata Toxicity: Data not available 

9 J Vapor ((tea) Irritant Charactartatlca: vapor ia modarataly mating auch that paraonnal w* nol 

uaually tolarata modarala or high concentrations. 

9.9 Uquid or SdW IntUttt Characteristics: Minimum hazard. H spiled on clothing and allowed 10 

remain, may cauaa smarting and reddening ol tha akin. 

9.10 Odor Threehokt 0.21 ppm 

9.11 IOLH Value: 10000 ppm 

t FIRE HAZARDS 

•.1 Fteeh PO M -38- F C.C: -58-F OC 

8J FlammaWa Umtta In Air 4H.-80* 

8J F_» EmngUaHng Agents: Ory chenscol. 

aJcohol loam, carton dionda 

9.4 Flra Cr_ngi_ar_ng Aganta Not to ba 

Used: Watar may ba nadoctiva 

9.9 Spadal Haiarda of ConmusBon 

Preducta: Producoa mtanng vapor whan 

haatad 

9.9 Behavior In Flra: vapora am haaviar than 

m and may traval a conaidarablo 

diatancatoa source of ignrtion and (lash 

back. 

97 ignmon Temperature: MS'F 

94 Electrical Hoard: Class 1. Group C 

9.9 Burning Rata: 3.3 mm/min. 

8.10 Adtobotlc Flame Temperature: 

Oala not avadable 

fCentftutdl 

7. CHEMICAL REACTIVITY 

7.1 Ra-cBvtty with Watar No raaction 

7.2 RaoctMly with Common MatarlalB: No 

reection 

7.1 StaMtty During Tranaport Stable 

7.4 Noutraa__ig Aganta for Adda and 

Couadcc Not portmant 

7 J PorymortiaBon: May occu. Avoid hen. 

dual, strong oxidizng or reducing 

substances, atrong adda and baaaa 

7M biMbitos of Pofymeftiedon: Nona 

7.7 Molar Ratio (Baactant to 

Product): Oata not tvaHabta 

7J naacttvtty Onup: 19 

I WATER POLUmOM 

9.1 Aquatic Toxicity: 

53 ppm/98 hr/sun«ah/T_./_eah watar 

70 ppm/24 hr/pin parch/TL^/aaR watar 

(_* Watartowl Toxicity: Oau not avaaacM 

SJ Btotoglcel Oxygon Oomend (BOO* 

93-127%. S days 

a.4 Food Chain Concentration Potential; 

9. SHIPPING INFORMATION 

9.1 Ondooof Purity: >gg% 

9.2 Storaga Tampaialma Ambiant 

9J Inorl Atmoopfiora: Inartad 

9.4 VanUng: Salaty rata) 

«. FIREHAZA 

8.11 Stolel-omauk. Air to Fual Ratio: 7 800 (Est 

9.12 Flama Temperature: Oata not availabia 

18. HAZARD ASSESSMENT COOE 

(Baa Haaard Meeaamenf Handbook) 

A-B-C-K-L-M-N-Z 

11.1 

t u 

11J 

12. 

12.1 

I 2 J 

i l l 

12.4 

12J 

12J 

12.7 

12J 

12J 

12.10 

12.11 

12.12 

12.11 

12.14 

12.18 

12.18 

12JS 

12J8 

12J7 

11. HAZARD ClASSirKATIONS 

Code of Federal Aegutattone: 

Flanwnabla kquM) 

NAS Hazard Rating tor But Watar 

Tranaportatlon: 

Cataffory Plating 

Rra 4 

Health 

Vapor imtant 3 

Poisons 2 

Watar PoMwn 

Human Toncrty 3 

Aquatic Toxicity 2 

Aesthetic Effect 3 

Reactivity 

Other Chemcats 2 

Watar 2 

Self Reactor. 0 

NFPA Hazard OaaaMcatton: 

Catagory Ctaaalflc atlon 

Haalth Hazard IBha) 2 

FlammabiMy (Rad) 4 

Raactwt, (Yat-wl 2 

PHYSICAL ANO CHEMICAL UtOKATI-S 

Phyaical Stata al 1i*C and 1 8tn: 

Ugud 

Molacular Walgftt 44.09 

BoMng Point at 1 atn. 

88.7-F - 20.4-C - 283.8'K 

Freezing Pone 

-189-F _ -123-C . 150-K 

Critical Tamparatura: 

370'F - 188*C - 481'K 

Critical Praaaura: 

920 paia . 58 atm . 9.7 MN/m> 

SpacMM Gravity: 

0.780 at _0*C (liquid) 

Liquid Surface Tanatonc Not paninant 

UquM watar tntarfadal Tanalon: 

Nol partinant 

Vapor (Oaa) Dpacine Oravlty: 15 

Ratio of Spadflc Hoata of Vapor (Oaa): 

1.192 

Latanf Haat of tam^mmt.mumm. 

245 8tu/lb - 138 cal/g -

5 69 X 10* J/kg 

Haat of Combuatlore -10.800 Btu/D 

. -5800 eal/g - -248.4 X to1 J/kg 

Haat of DaconipoaHlon: Not pamnont 

Haat of SolutlOff Not parbnant 

Haat of PotytnarlmtafE Not portviant 

Haal of Fuatarc Oata not avaNabla 

Umftlng Value: Oata not available 

Raw Vapor Praaaura: 25.8 paia 

R0S (Continued) 

) 

JUNE 1985 
P.53 

12.17 

SATURATED UOUID DENSITY 

Temperature 

(degrees F) 

- 2 0 

—10 

0 

10 

20 

30 

40 

50 

60 

Pounds per cubic 

foot 

52.490 

52.060 

51.630 

51.200 

50.770 

50.340 

49.910 

49.480 

49.050 

12.18 

UOUID HEAT CAPACITY 

Temperature 

(degrees F) 

—100 

—80 

- 6 0 

—40 

—20 

0 

20 

40 

60 

British thermal unit 

per pound-F 

.297 

.300 

.304 

.308 

.311 

.315 

.319 

.322 

.326 

12.19 

UOUID THERMAL CONDUCTIVITY 

Temperature 

(degrees F) 

28 

30 

32 

34 

36 

38 

40 

42 

44 

46 

48 

50 

52 

54 

56 

58 

60 

62 

64 

66 

68 

British thermal 

unit-inch per hoursquare foot-F 

1.317 

1.314 

1.311 

1.307 

1.304 

1.301 

1.297 

1.294 

1.291 

1.287 

1.284 

1.281 

1.277 

1.274 

1.271 

1.267 

1.264 

1.261 

1.258 

1.254 

1.251 

12.20 * 

UQUID VISCOSITY 

Temperature 

(degrees F) Centipoise 

N 

O 

T 

P 

E 

R 

T 

1 

N 

E 

N 

T 

12_21 

SOLUBILITY IN WATER 

12.22 

SATURATED VAPOR PRESSURE 

12_23 

SATURATED VAPOR DENSITY 

12.24 

IDEAL GAS HEAT CAPACITY 

Temperature 

(degrees F) 

Pounds per 100 

pounds of water 

Temperature 

(degrees F) 

Pounds per square 

inch 

Temperature 

(degrees F) 

Pounds per cubic 

foot 

Temperature 

(degrees F) 

British thermal unit 

per pound-F 

M 

I 

S 

C 

I 

B 

L 

E 

0 

5 

10 

15 

20 

25 

30 

35 

40 

45 

50 

55 

60 

65 

70 

75 

80 

85 

90 

95 

100 

105 

110 

115 

120 

125 

2.704 

3.111 

3.567 

4.080 

4.652 

5.291 

6.002 

6.790 

7.664 

8.629 

9.693 

10.860 

12.150 

13.560 

15.100 

16.780 

18.610 

20.610 

22.770 

25.120 

27.660 

30.400 

33.360 

36.560 

39.990 

43.680 

0 

5 

10 

15 

20 

25 

30 

35 

40 

45 

50 

55 

60 

65 

70 

75 

80 

85 

90 

95 

100 

105 

110 

115 

120 

125 

.02414 

.02747 

.03117 

.03527 

.03980 

.04460 

.05029 

.05633 

.06294 

.07016 

.07804 

.08661 

.09593 

.10600 

.11700 

.12880 

.14150 

.15520 

.17000 

.18580 

.20280 

.22090 

.24030 

.26100 

.28310 

.30660 

0 

20 

40 

60 

80 

100 

120 

140 

160 

180 

200 

220 

240 

260 

280 

300 

320 

340 

360 

380 

400 

420 

440 

.269 

.276 

.263 

.290 

.298 

.305 

.312 

.319 

.326 

.333 

.339 

.346 

.353 

.360 

.366 

.373 

.379 

.386 

.392 

.398 

.405 

.411 

.417 
sr-ftt-33* 

c.a 

HANDBOOK OF 

TOXIC AND HAZARDOUS 

CHEMICALS AND 

CARCINOGENS 

Second Edition 

iaging 

rocess 

jnt de 

.orpo-

*. Uniby 

Marshall Sittig 

Princeton University 

'3*55" 

np NOYES PUBLICATIONS 

Park Ridge, Maw Jersey, USA. 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK, NC 
•^r-Kjj*-.; IJW H **'B,1«B5* -^ssf^'r*-' ^^f- w 

Acetaldehyde 21 

References 

(1) U.S. Environmental Protection Agency, Acenaphthene: Ambient Water Criteria, 

Report PB 296-782, Washington, OC (1980). 

(2) Sax, N.I., Ed., Dangerous Properties of Industrial Materials Report, 4, No. 1, 38-41, 

New York, Van Nostrand Reinhold Co. (1984). 

ACENAPHTHYLENE 

See "Polynuclear Aromatic Hydrocarbons." 

ACETALDEHYDE cM3CMO 

o Hazardous substance (EPA) 

o Hazardous waste (EPA) 

Description: CH3CHO, acetaldehyde, is a flammable, volatile colorless liquid 

with a characteristic penetrating, fruit odor. It boils at 20° to 21°C. 

Code Numbers: CAS 76-07-0 RTECS AB 1925000 UN 1089 

DOT Designation: Flammable liquid. 

Synonyms: Acetic aldehyde, aldehyde, ethanal, ethyl aldehyde. 

Potential Exposure: Acetaldehyde can be reduced or oxidized to form acetic 

acid, acetic anhydride, acrolein, aldol, butanol, chloral, paraldehyde, and pentaerythritol. It is also used in the manufacture of disinfectants, drugs (A-41), dyes, 

explosives, flavorings, lacquers, mirrors (silvering), perfume, photographic 

chemicals, phenolic and urea resins, rubber accelerators and antioxidants, 

varnishes, vinegar, and yeast. It is also a pesticide intermediate (A-32). 

NIOSH estimates that 2,430 workers are exposed to acetaldehyde. Acetaldehyde is the product of most hydrocarbon oxidations; it is a normal intermediate 

product in the respiration of higher plants; it occurs in traces in all ripe fruits 

and may form in wine and other alcoholic beverages after exposure to air. 

Acetaldehyde is an intermediate product in the metabolism of sugars in the body 

and hence occurs in traces in blood. It has been reported in fresh leaf tobacco as 

well as in tobacco smoke and in automobile and diesel exhaust (A-5). It has been 

found in 5 of 10 water supplies surveyed by EPA with the highest concentrations in Philadelphia and Seattle at 0.1 mli (A-2). 

Incompatibilities: Strong oxidizers, acids, bases, alcohol, ammonia, amines, 

phenols, ketones, HCN, HfeS. 

Permissible Exposure Limits in Air: The Federal standard (TWA) is 200 ppm 

(360 mg/m3); however, the ACGIH 1983/84 recommended TLV is 100 ppm 

(180 mg/m3). The tentative S.TEL is 150 ppm (270 mg/m3) and the IDLH level 

is 10,000 ppm. 

Determination in Air: Acetaldehyde may be collected by impinger or fritted 

bubbler and then determined colorimetrically (A-8). 

Permissible Concentration in Watar: Human exposure to acetaldehyde probably antedates recorded history, inasmuch as acetaldehyde is the major metabo-
22 Handbook of Toxic and Hazardous Chemicals and Carcinogens 

lite of ethyl alcohol. An additional source of widespread human exposure is 

tobacco smoke. The pharmacology and toxicology of acetaldehyde have been 

studied most extensively in its relationship to alcohol toxicity and human metabolism. Because of this background of human and laboratory experience, there 

appears to be no need to establish limits for acetaldehyde in drinking water 

(A-2). However, EPA (A-37) has set an ambient environmental goal of 2,480 

/j.g/2 for acetaldehyde on a health basis. 

Routes of Entry: Inhalation of vapor, ingestion. 

Harmful Effects and Symptoms: Local - The liquid and the fairly low levels 

of the vapor are irritating to the eyes, skin, upper respiratory passages, and bronchi. Repeated exposure may result in dermatitis, rarely, and skin sensitization. 

Systemic - Acute involuntary exposure to high levels of acetaldehyde vapors 

may result in pulmonary edema, preceded by excitement, followed by narcosis. 

It has been postulated that these symptoms may have been similar to those 

of alcohol, which is converted to acetaldehyde and acetic acid. Chronic effects 

have not been documented, and seem unlikely, since voluntary inhalation of 

toxicologically significant levels of acetaldehyde are precluded by its irritant 

properties at levels as low as 200 ppm (360 mg/m3 of air). 

Points of Attack: Respiratory system, lungs, skin, kidneys. 

Medical Surveillance: Consideration should be given to skin, eyes, and 

respiratory tract in any preplacement or periodic examinations. 

First Aid: If this chemical gets into the eyes, irrigate immediately. If this 

chemical contacts the skin, flush with water promptly. If a person breathes 

in large amounts of this chemical, move the exposed person to fresh air at 

once and perform artificial respiration. When this chemical has been swallowed, 

get medical attention. Give large quantities of water and induce vomiting. Do 

not make an unconscious person vomit. 

Personal Protective Methods: Wear appropriate clothing to prevent repeated 

or prolonged skin contact. Wear eye protection to prevent any possibility of eye 

contact. Employees should wash promptly when skin is wet. Remove clothing 

immediately if wet or contaminated to avoid flammability hazard. Provide eyewash. 

Respirator Selection (A-4): 

1,000ppm: CCROVF 

5,000 ppm: GMOVc 

10,000ppm: GMOVfb/SAF/SCBAF 

Escape: GMOV/SCBA 

Disposal Method Suggested: Incineration (A-31). 

References 

(1) U.S. Environmental Protection Agency, Chemical Hazard Information ProfHe: Acetaldehyde, (Preliminary), Washington, DC (1979). 

(2) U.S. Environmental Protection Agency, Acetaldehyde, Health and Environmental 

Effects Profile No. 1, Washington, DC, Office of Solid Waste (April 30,1980). 

(3) Sax, N.I., Ed., Dangerous Properties of Industrial Materials Report, 1, No. 1, 25-6

New York, Van Nostrand Reinhold Co. (1980). 

(4) See Reference (A-61). 

(5) See Reference (A-60). 

(6) U.S. Environmental Protection Agency, Chemical Hazard Information Profile Draft 

Report: Acetaldehyde, Washington, DC (April 29,1983). 
_ . P.57 

tmaammmmmmmi^^tmmmmt^a^mmi^tmm^^ 

INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 84 

Acetaldehy4fiL_-.(Wacker process) 

C2H4 + 1/2 02 >-\CH3CHOU heat (244 kJ/mole) 

Function - The Wacker process employs an aqueous catalvst solution 

of palladium chloride, promoted by copper chloride. 

The catalyst acts as the oxygen carrier and causes selective 

conversion of ethylene to acetaldehyde. The reaction steps essentially 

are: 

PdCl, 

Reaction: C,H. + 2CuCl„ + Ho0 =-+• CH,CHO + 2HC1 + 2CuCl 

2 4 2 2 3 

Regeneration: 2CuCl + 2HC1 + l/202 • 2CuCl2 + H20 

There are two basic process variations, depending upon such factors 

as oxygen cost, utilities prices, and available ethylene purity. 

In the single-stage process, pure oxygen is employed as the oxidant. 

The reactor effluent is condensed and water-scrubbed. Unreacted 

gas is recycled into the reactor. By-products and water are separated 

from the acetaldehyde product by distillation. Both the reaction 

and regeneration are effected at the same time. 

In the two-stage process, the oxidant is air. The reaction is 

^ [ carried out with catalyst solution and ethylene in one reactor, and 

X * the regeneration is carried out with air in a separate reactor. Lower 

ki purity ethylene can be used with this version of the process. However, 

/ this process forms more by-products and requires high operating pressures. 

The production of acetaldehyde by vapor phase oxidation of propane" 

rich LPG is considered obsolete. 

2. Input Materials (per metric tonne acetaldehyde) 

6-236 
Ethylene 99.8 vol. %, kg 

3 

Oxygen, Nm 

Catalyst: PdCl2, g 

CuCl2 + 2H20, g 

HCl (100%) used as 30% aqueous 

solvent, kg 

3. Operating Parameters 

Temperature, °C(°F) 

Pressure, kPa (atm) 

4. Utilities 

3 

Cooling water (25°C), m 

3 

Cooling water (12°C), m 

3 

Process water, m 

3 

Deionized water, m 

Steam, metric ton 

Electric power, MJ (kWh) 

Credit for nitrogen (protection 

gas), Nm-3 (637 kPa) 

to flare (air). 

Single-stage 

670 

275 

0.9 

150 

4 

130(266) 

294 (2.90) 

300 

-

6 

3 

1.6 

754 (210) 

Ethane: 2.2 kg/Mg acetaldehyde 

Ethylene: 27.4 kg/Mg acetaldehyde 

Acetaldehyde: trace 

Methane: trace 

Methyl chloride: trace 

Two-stage 

* 

670 

-

0.9 

150 

15 

-

784-883 

(7.74-8.71) 

200 

12 

-

-

1.2 

** 

300 

900 

Ethylene of lower purity results in slightly higher consumption 

** 

Including air compression 

6-237 
P.59 

Purification section - acetaldehyde stripper vent to flare (air) 

Methyl chloride: 8.65 kg/Mg acetaldehyde 

Acetaldehyde: trace 

3 

A typical Wacker process discharges about 4.4 m (1,200 gallons) 

of waste per ton of product. The chlorinated aldehydes are the 

principal contaminants in the waste streams which have a COD of 

3 

approximately 10 cg/m (10,000 mg/1). 

The two-stage process yields relatively small amounts of a 

rather concentrated waste water which must be pretreated before 

normal biodegradation. The single-stage yields considerably more 

of a more dilute waste water suitable for biodegradation. 

6. EPA source classification code - None 

7. References 

Morse, P. L., "Acetaldehyde," Report No. 24, Stanford Research 

Institute, Menlo Park, California, April 1967. 

Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional 

Problems Associated with Petrochemical Wastes," for FWPCA, Contract 

No. 14-12-461, February 1970. 

Austin, G. T., "The Industrially Significant Organic Chemicals -

Part 1," "Chemical Engineering," January 21, 1974, p. 127. 

"1975 Petrochemical Handbook," "Hydrocarbon Processing," 54^, November 

1975, p. 100. 

Jira, R., et al., "Hydrocarbon Processing," 55_, March 1976, p. 99. 

6-238 
INDUSTRIAL ORGANIC CHEMICALS PROCESS NO. 124 

Acetaldehyde (from ethanol) 

CH3CH2OH + 1/2 02

 A£ -* CH.CHO + H20 

1. Function - As of 1974, only 15% of the United States acetaldehyde 

capacity was based on ethanol. There are two processes for conversion 

of ethanol to acetaldehyde, i.e., oxidative dehydrogenation and 

catalytic dehydrogenation. 

Oxidative dehydrogenation 

The vapor phase reaction is carried out over solid silver gauze 

catalyst at 538°C (1000°F). Aqueous ethanol, steam, and air are 

fed to the oxidizer (reactor). The reactor effluent is condensed 

^^_____________----_^M___^^_» 

and is passed to a phase separator which also serves as a scrubber 

(refrigerated water). The off gases are vented from the system and 

the wash is combined with the liquid stream. The combined liquid 

stream is sent to a flash column where it is separated into acetaldehyde product, alcohol for recycle, and waste water. The acetaldehyde 

product from the flash column is sent to an ethanol recovery still 

where acetaldehyde product is taken from the top and the bottoms 

(primarily ethanol) are recycled to the reactor. 

Catalytic dehydrogenation 

The primary reaction is: 

CH3CH2OH -*=-•• CH3CHO + H2 

The vapor phase reaction is carried out over a solid copper 

catalyst promoted by cobalt or chromium on an asbestos support at 

260°C (500°F). The recovery and isolation systems are almost identical 

to those in oxidative dehydrogenation. The yields in both processes 

range from 85 to 95%. 

6-324 
h 

P.61 

L 

2. Input Materials 

Oxidative dehydrogenation: air 

ethanol 

steam 

water 

Catalytic dehydrogenation: ethanol - 1150 kg/metric ton (2,535 lbs/ton) 

acetaldehyde 

3. Operating Parameters 

Oxidative dehydrogenation: temperature - 538°C (1000°F) 

pressure - 410 kPa (4.05 atm) 

flow rate - not given 

equipment - multitubular reactor, 

phase separator, flash 

column, still 

catalyst - solid silver gauze 

Catalytic dehydrogenation: temperature - 260°C (500°F) 

pressure - not given 

flow rate - not given 

equipment - see oxidative 

dehydrogenation 

catalyst - solid copper catalyst 

promoted by cobalt or 

chromium on an asbestos 

support 

4. Utilities - The water usages of two plants are: 

Process water Cooling water 

Plant 1 5.9 kg/kg product 47.2 kg/kg product 

Plant 2 0.45 kg/kg product 45.4 kg/kg product 

6-325 
P.62 

•Hi 

Waste Streams 

Air - Off gases from the phase separator; it has been estimated that 

12.2 Mg (27 MM lb) of CO is emitted annually from this industry. 

Water - The only wastewater stream generated is either from the 

acetaldehyde flash column or ethanol recovery still. It contains 

liquid products such as acetaldehyde, ethanol. and ethyl acetate. 

Data on two plants (one using each of the two processes) was as 

follows: 

Plant 1 

Flow 

COD 

BOD 

6.0 mJ/ 

454 kg 

product 

0.186 kg/m3 (186 

mg/1) 1.1 kg/454 

kg 

0.084 kg/m3 (84 mg/ 

1) 0.50 kg/454 kg 

Plant 2 

529 dm3/ 

454 kg 

product 

TOC 14.4 kg/mJ (14,400 

mg/1) 7.6 kg/454 

kg 

6. EPA Source Classification Code - None 

7. References 

Austin, G. T., "Industrially Significant Organic Chemicals -

Part 1," "Chemical Engineering," January 21, 1974, p. 128. 

6-326 
P.63 

£EFtt 

United States 

Environmental Protection 

Agency 

Office of Air Quality 

Planning and Standards 

Resesrch Triangle Park NC 27711 

TtZ 

EPA-450/3-80-028d 

December 1980 

Air 

Organic Chemical 

Manufacturing 

Volume 9: Selected 

Processes 

miwwi" T 
III-l 

III. PROCESS DESCRIPTION 

INTRODUCTION 

In the United States 94.9% of the acetaldehyde capacity is based on the HoechstWacker process, which consists of two-step air oxidation of ethylene. Approximately 4.7% is based on oxidation of ethanol, and the remaining 0.4% is recovered 

as by-product from other processes. Hydration of acetylene and oxidation of 

saturated hydrocarbons (butane and propane), once processes of major importance 

in the United States, have given way to the more economic ethylene-based process. 

A rhodium catalyzed process capable of converting synthesis gas directly into 

2 

acetaldehyde in a single step was reported in 1974. This process may become 

important in the future as coal gasification methods are perfected. 

B. ACETALDEHYDE FROM ETHYLENE 

The direct liquid-phase oxidation of ethylene to acetaldehyde by means of a 

palladium chloride-cupric chloride catalyst was discovered in 1956. The commercial process was developed and licensed by the consortium of Hoechst and 

Wacker in Germany in the late 1950s and early 1960s. Since 1960 all reported 

4 

new plants have used the Hoechst-Wacker technology. 

Direct oxidation of ethylene to form acetaldehyde is accomplished through a 

series of oxidation-reduction reactions. The catalyst is an aqueous solution 

of palladium chloride and cupric chloride. The reaction of ethylene with an 

aqueous palladium chloride solution to form acetaldehyde is represented by Eq. (1) 

C2H4 + PdCl2 + 

(ethylene) (palladium 

chloride) 

H20 

(wate 

CH CHO Pd + 2HC1 (1) 

(acetaldehyde) (metallic (hydrochloric 

palladium) , acid) 

The palladium is reoxidized to palladium chloride by cupric chloride as shown 

by Eq. (2). 

Pd + 2CuCl. ->• PdCl„ + 2CuCl 

2 

(2) 

(palladium) (cupric chloride) (palladium (cuprous chloride) 

chloride) 
P.65 

Review Draft 

EPA-450/3-87-026 

I 

I 

I Hazardous Waste Treatment Storage and Disposal 

Facilities (TSDF) — Air Emission Models 

Emission Standards Division 

U.S. ENVIRONMENTAL PROTECTION AGENCY 

Office of Air and Radiation 

Office of Air Quality Planning and Standards 

Research Triangle Park NC 27711 

July 1990 
cn-rato NME CAS | M.W. 

D84SITY VAP.PRESS SOUBILnY H LAW CONST.DIFF.HUB* 

(Q/NC ) (fmha) («B/I) (ataMra/Mol) (cnfi/Mc) 

BOILING 

DDT.AIR POINT 

(a£/Nc)(<hg.C) 

VAPOR PRESSURE COEFFICBENTS 

S-VU__N0kETMtL-3-ISOXAZ0La_ 2769-86-4 114.1 

6-OfjORO-l,3-CYCLOP_HrAD_BC 246 100.00 

6-HYDR0KY-l,3-C.CLOPB*ITAOIBC 728 61.00 

6-ME1HYl_FURRfiAL 620-02-0 110.11 

6-iEnm.-i,3-cYa_aPENrADiBc 26619-91-6 80.14 

Kamam*. 86-32-9 1M.21 1.07 

ACBWHTWABC 208-86-8 168.21 

ACETAUDBIYDE 7S-07-0 44.0 0.79 

ACETAMIDE 60-36-6 68.07 

ACETIC ACID 64-19-7 60.06 1.06 

ACETIC ANHYDRIDE 108-24-7 102.09 1.04 

ACEIOE 67-64-1 68.08 0.79 

AOEIDE 76-06-8 68.0 0.79 

ACETONITRILE 76-06-8 41.08 0.78 

ACETOPHB-OC 96-86-2 120.16 1.08 

ACETYL OUORIDE 7»-36-6 78.60 1.11 

ACETYL DIETHVU-ALOrttTE 266 194.00 

ACETYUENE 74-86-2 26.04 

ACROLEIN 107-02-6 66.1 0.84 

ACRYLAMIDE 79-06-1 71.09 O.OO 

ACRYLIC ACID 79-10-7 72.10 0.00 

ACRYLONITRILE 107-18-1 68.1 0.81 

AOWIUNTANE DICARBOXYLIC ACID 828-61-8 180.26 

AQAMWfTANE DICHLORIDE 171 207.10 

ADIPIC ACID 124-04-9 146.14 1.87 

AUHCAR8 116-06-3 190.29 

ALDRIN 609-00-2 864.98 

ALLYL ALCOHOL 107-18-6 68.1 0.86 

ALLYL CHLORIDE 107-O6-1 78.68 0.94 

ALPHA METHYL STYRBC 98-88-9 118.00 O.OO 

AlPHA IETHVL STYRBE DDJERS 88 236.00 

•lph»-CHL0RO-b«U-ICTHYt_NAPHlH86-62-2 178.66 

ALPHA-HYDRQXYACETALDB1YDE 60 

ALPHA-HYDRQXYM)IPIMIDE 429 162.00 

•Ipha-METHYLSTYRBE (-4) 98-93-9 118.19 

• iphfr-PICOLIhE 1333-41-1 93.14 

0.1 

O.006 

780 

1 

16.41 

6.286 

266 

266 

90 

1 

287.8 

200 

0.2 

2 

60000 

0.2 

2 

2 

680000 

IOOO 

40 1086 

244.2 

0.012 

6.2 6.17E-07 

114 

4 2 

0.2 

O.0000226 

28.8 

0.076 

6000 

0.01 

100 

2 

2 

2 

IOOO 

2 

20000 

7.61E-C6 

E.OOE-OS 

4.06E-06 

2.20E-O7 

4.01E-0B 

7.71E-08 

1.14E-04 

9.GOE-06 

1.20E-O7 

6.27E-0B 

6.91E-06 

2.60E-06 

2.60E-O6 

6.80E-06 

1.41E-06 

O.OOE-tOO 

1.94E-05 

1.26E-08 

6.66E-06 

6.20E-1O 

l.OOE-07 

6.80E-06 

1.O4E-03 

6.08E-U 

8.17E-06 

8.66E-02 

1.80E-06 

3.71E-01 

6.91E-08 

1.18E-02 

8.83E-08 

9.G0E-06 

1.62E-06 

6.91E-03 

4.66E-0I7 

O.OOE«00 O.OOEOO 278.0 7.728 2634.234 246.676 

1.41E-05 1.24E-01 20.8 8.006 1600.017 291.809 

1.20E-06 

9.33E-06 

1.14E-06 

1.14E-06 

1.66E-06 

O.00E«OO 

1.16E-06 

l.lSE-Ol 

2.86E-01 

1.24E-01 

1.24E-C1 

1.28E-01 

O.00E«O0 

9.90E-O2 

1.22E-06 1.06E-O1 

1.06E-06 9.70E-O2 

1.06E-06 9.60E-O2 

1.34E-06 1.22E-01 

0.84E-O6 6.69E-02 

1.14E-06 1.14E-01 

O.OOE«00 O.00E«O0 

1.14E-06 2.64E-01 

118.0 7.387 1638.818 222.309 

139.6 7.149 1444.718 199.817 

66.2 7.117 1210.696 229.664 

G6.2 7.117 1210.696 229.664 

81.6 7.119 1314.4 280 

202.3 9.136 2878.8 273 

E2.0 6.948 1116.964 223.664 

63.0 2.387833 

87.0 O O O 

141.6 6.662 648.629 164.683 

77.4 7.038 1232.63 222.47 

266.0 

97.0 1.367406 

46.0 O 

-38.8 6.923 1486. 

O O 

202.40 
*•# ] 

• Estimate the biodegradation rate constants using the following 

methodology: 

Approximate K^ax fro* available data for K^ * for compounds 

of similar structure and/or functional groups; and 

Approximate Ki either by using the following correlation: 

KjU/h/g) - 0.135 KQW 0.38 

where K - octanol-water partitioning coefficient 

or by using the default (average) value for K\, which is K\ 

* 1 L/h/g, and then calculate Ks as: Ks * Kmax-^lThe following properties are given for each chemical (listed by name 

and Chemical Abstract Source [CAS] number): 

Molecular weight 

Density 

Vapor pressure at 25 *C 

Solubility 

Henry's law constant 

Diffusion coefficient in water 

Diffusion coefficient in air 

Boiling point 

Coefficients for the Antoine equation for estimating vapor 

pressure at temperatures other than 25 °C. 

To estimate vapor pressures at temperatures other than 25 *C, the 

Antoine equation coefficients are used with the following equation: 

log/jQV Vapor Pressure (mm Hg) » A J_ 

where 

A, B, and C • the Antoine equation coefficient 

T » temperature in *C. 

Two approaches may be used to introduce a new compound and its 

properties into CHEMDAT7. First, the data for one compound in 

CHEMDAT7 may be replaced with data for the compound of interest in the 

D-7 
w 

P.68 

columns specified above. With this approach, the list of compounds in 

CHEM0AT7 remains constant at 62. The second approach involves appending the new compound an1 Its properties to the existing list of chemicals in CHEMOAT7. All the equations/calculations must then be copied 

from one of the existing rows via Lotus 1,2,3 into the appropriate 

cells in the new row of the spreadsheet. As mentioned above, the 

inclusion in CHEM0AT7 of all or a large part of the chemicals listed 

in this appendix could result in increasing the time required to exercise CHEMDAT7 and could prevent its use on some microcomputers. 

The properties of interest listed above, with the exception of 

the CAS number, mimic those in columns B, D-M, and Q of the CHEM0AT7 

spreadsheet. 

D-8