p.1 

OAR Box 1877 

Prepped by Keeia Richards 

Document Number: 

8) ll-B-5 

Docket Number: 

A-90-19 

Printed 12/2/200810:36:46 AM Sheet 8 of 46 
P.2 

A-90-19 

ll-B-5 

MEMORANDU M 

TO: 

FROM: 

DATE: 

Process Vents Docket A-90-19 

Wanda Floyd 

October, 1990 

IMJLU I 

SUBJECT: HON NESHAP: Industry Characteristics/Acetic Anhydride 

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

Anhydride via Cardonylation of Methyl Acetate, via air oxidation of 

Acetaldehyde, and via Dehydration of Acetic Acid 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. 

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

pp. 428-429. 

Lowenheim, Fredrick A. et. al. Faith. Keyes and Clark's Industrial Chemicals. 

4th edition. John Wiley & Sons, New York, 1975. pp. 16-20. 

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

Verlag Chemie, New York, 1978. pp. 160-163. 

Kent, James A. Riegel's Handbook of Industrial Chemistry. 7th edition. Van 

Nostrand Reinhold Company, New York, 1974. p. 791. 

Meyers, Robert A. Handbook of Chemicals Production Processes. McGraw-Hill 

Book Company, New York, 1986. pp. 1.1-3 to 1.1-8. 

Wiseman, Peter. An Introduction to Industrial Organic Chemistry. 2nd edition. 

Applied Science Publishers LTD, London, 1979. pp. 103-104. 

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

Wiley & Sons, New York, 1985. pp. 10-11. 

Austin, George T. Shreve's Chemical Process Industries. 5th edition. 

McGraw-Hill Book Company, New York, 1984. p. 768. 

Shreve, R. Norris and Brink, Jr., Joseph. Chemical Process Industries. 4th 

edition. McGraw-Hill Company, New York, 1977. p. 709. 

Ine Corresponding Oaaiity Assurance A-90-1 9 

Document is Docket Item

 nB"252 
P.3 

a 

. //fe-/c/.' /Ja.loJi.' Preparer: 

Oate: s-n-io 

Reviewer: 

P>oduct~fcroce$$ Cfcte 

ADMINISTRATIVE NOTES 

/O^lH-1 Pr 

Hours spent on this PPS %-0 L'J 

P-P Name ACETIC ANHYDRIDE V'Oa -=?,V OX/Jof/oy- » / qcefa/d^n/e 

Incomplete Items (parts of 

form you cannot complete) 

(line # and description) 

<W /• 7 

Pate Cleared, Initials 

Chemicals missing CAS numbers 

acetyl ^h^t l$olo 

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

ri Q ^ ° 
P.4 

Preparer: /l^/iclO /VycXbaJ-/ 

Date: g- 1-7-40 

Reviewer: 

Chemical Nanta 

PRODUCT-PROCESS SUMMARY (PPS) 

o. ctf: c ^ *i Ii .i dxj £ 

Alternative Cfttoticif'IftM 

CAS I * gS

 2L H 

CHEMICAL SPECIFIC INFORMATION 

ZLttll oxiJl 

o ol 

1.0 U.S. Production Ref # ., Pg # ., Ref Year 

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

different reference) 

I.r "IB«lFfmim(HM i dtff unions of ko^or millions of gal fans 

^%\ i°&\ 

ttXw>w>K4W>;<<cw&>x*w>>x<?R!M 

11111 

f\Cr cic-^< '^-6^- d.4lt &r 

•s 

r 

v*. 

V \ 

fV ^ -

1 s/Kg or s/qallQn 

A" *U>6 

1.8 Comments 
Use Pattern 

P.5 

2.0 Chemical End-Use Ref # Jh__ , Pg # ' ^ - Ref Year "7 5 

_Uje_ Percent 

Cellulose esters (including cellulose 

acetate, acetate butyrate, and 

acetate propionate) 

Aspirin 

Miscellaneous 

Percent 

95 

100 

•i 3 
3.0 U.S. Producers Ref # _ 9 , Pg # Maff Ref Year j £ 

3.2 Name, Location, and Capacity 

H°ecKe> CeUwv e ^ d 

<A/^»<\ <xr^t^~t 

Process Used 

(use P-P #) JnTi-s KJ* 5 

R»cK Wl/ , S.C . 

fe r©u>f\s v/»l'W "*~ K. 

H ^ P/7-? 

p P ^ P?xi 

¥-?2_ 

2U.* f 

»l*.li 

£££^-2=- f/>.!!. 

m .JZ 

Total Capacity l°l* > / 

vJWteO?.'!^... 

b> 
P.7 

PRODUCT.PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) 

Name 

,p 2 debjar-ifOoy.o'f aCeAc <*c/e/ 

•p 3 '^W (AU^ji &Li j'.^n Vl— 

-P 4 Co.rior\, .Idrfvr. <yv ftvejy cr^t ^ 

-P 5 

-P 6 

.1 Documentation of P-Ps Excluded 

P-P not 

Commercially Viable 

Ref # ll 

., Pg # ^ 

Commercially % Nat'l 

Viable (y/n) Capacity 

*_ ^L&"*0 

_Z_ ^-S^* Or5^ 

if: 

X. 

Reasons 

£X 

*Ce/7c <U^J < <* 
P.8 

C3T SlKNttTi *M* 

d Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenation Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenation Reaction 

Sulfonation Reaction 

Catalytic Reformation 

Hydrodlmerlzatlon Reaction 

Ref I Pg # ) ( 

Generic Reaction 

4.4 Explain how you selected the reaction type in Un e 4.3. 

Qu€ t *dt>'» ^ *W* ' QX 
P.9 

it 

4.5 Written Description 

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

description. 

Process 

Air is bubbled through liquid acetaldehyde in a reactor in the 

presence of 2% (based on the weight of acetaldehyde) catalyst, such as a 

mixture of copper and cobalt acetates or manganese acetate, which 

prevents the formation of explosive amounts of peracetic acid. Approximately 1.4 parts of acetic acid per 1 part of acetaldehyde is 

present as a diluent to promote acetic anhydride formation. Methyl or 

ethyl acetate, triacetin, or benzene may also be used as a diluent, and 

the last is generally utilized in conjunction with acetic acid as a 

withdrawing agent in subsequent vacuum distillation to allow separation of the reaction mixture from water at lower temperatures. | 

The reactor is maintained at a temperature of 50 to 70° C, and the 

pressure is approximately 60 psi (410 kPa). The overheat from the 

crude vacuum column is fractionated in an aldehyde column, yielding 

acetaldehyde for recycle as the overhead and water and diluent as bottoms. The diluent is returned to the reactor after the water is separated. 

The dehydrated mixture of acetic anhydride and acetic acid from the 

bottom of the crude vacuum column is separated by distillation. Acetic 

acid is removed as overhead, and the acetic anhydride is withdrawn 

from a bottom plate. The catalyst is taken from the bottom to be 

reused. The acetic anhydride may be further purified by vacuum distillation. 

Variations of this process involve type and amount of diluent, and 

several stages in the reactor (with oxygen injection into each stage) 

under milder reaction conditions. 

Present trends are away from air and toward oxygen. In one 

continuous process using ethyl acetate as the diluent and a catalyst 

concentration of 1% (cobalt acetate and copper acetate in a weight ratio 

of 2:1), the reaction is carried out at 50°C and 45 psi (310 kPa). 

Oxygen is injected at various points along the path of liquid travel, with 

the overall oxygen supply limited to 1 to 2% excess. Under these conditipjns^95%^ conversions of acetaldehyde are obtained. Both acetufanhydride and acetic acid are produced in a 50:50 weight ratio. 

The same process when carried out in the absence of the diluent gives 

a higher oxidation rate but yields a lower acetic anhydride/ acetic acid 

ratio (ca. 2:3). 
P.10 

From Acetaldehyde 

Wittf Nitrogen . 

ActBldihydt , 

C«Uly»t 

Diluent A"" XI 

RMCto etor|_ ^ 

AotakWiydt 

I 

•Wttiydt 

column 

J>£»22JESLa$E_ 

r Antic 

Kid 

f 

T 

•Acttle 

C«taty« 

r*tum 

5 

/ 

4-y.fcU ^~ * ^/r"

 a 'J sfy< 

5.0 Process Flow Diagram (attach at end of package) 

) 2. 5.1 Flow Diagram Reference: Ref # 

5.2 Comments on Flow Diagram 

., Pg * \£ 

Component Types 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

Ref I 

o 

o 

o 

"V 

1 

, Pg * 
P.11 

ACETIC ANHYDRIDE 

(CH,CO),0 

6.0 Chemical Data 

I 2- J / 

6.1 Balanced Chemical Reactions Ref # Pg # _ 

Reaction 

CH3CHO + 08 -• CH3COOOH 

CH3COOOH + CH3CHO -> (CH3CO) aO + H20 

70-757o yield 

6.2 Chemical Tree Ref # _i_3_ , Pg # i< 

-it 

J 

-f 
P.12 

-rUMMil 

6.4 Stoichiometry Ref #» ^ ' ^ .Pa - . pg # , '^ 

Show calculations and assumptions and then summarize in table on next 

page. 

<0% + ^ * lot y | 2 

k 

I 

<9 z - *-n 

Material Requirements 

Basis—1 metric ton acetic anhydride 

Acetaldehyde 

Catalyst 

Diluent (less recovery) 

Air 

1200 kg 

1kg 

1650 kg 

Variable 
P.13 

ttf a ?-U 

6.4 Stoichiometry Conversion Factors 

°) WLW^f^^m for CW 

d.~/o -.75" 

•ZS&Z 

•.t tt * tf Wf. t tst">t t t * .w/M^ n 

d) con^r$twF«tfdr'forC^l>lMra| 

tt. tt ttt t ttttt mtt yttttt <r tttsto. sHv t ttt t *sv w vt. V^AVAVWMWAW W 

e) Cdnvfrsfon *fccfor for CO-Pro^^H 

" A*. VAVAVA •> t \ %-W V W W . H --A S WAWwC-JvJ-WC 

f) Conversion Factor Comments 

< > - 75> 

k o»€V<y , h<H»f t»tujs *„ C^a; , /r9m * l V c V 

1 
P.14 

6.4.1 Product 

/f Ce /vc o* A^rfjr; J f 

6.4.2 Raw Material(sl 

#1 

#2 

#3 

#4 

#5 

OyCtfCyLctil 

o*33 

6r4t3 Co-Products 

#1 

#2 

#3 

#4 

#5 

6.4.4 Bv-Products 

#1 */y f* ^ 

#2 

#3 

#4 

#5 

v,4-5 

#1 

n 

Intermediates 

^ 

€ ^ 

IOVZHJ 

17 ^2^7 

lines' 

xi 

o-\L 

1% 
P.15 

11 i II umit 

7.0 Process Vent Emission Sources 

7.1 Are there process vent emissions? / (Y/N) 

7.2, A1r Oxidation vent m.ssions? Y (Y/N) Ref # )2 

., Pg * U 

7.3 Comments Ref I .. Pg # 

i 

nt. 2- (Y/N) 

Cylyl *~Q 

Ref # __ , Pg # 

7.5 Comments Ref I ., Pg # 
P.16 

n 

7.s at? 

7.7 8wa8eWl 

7.8 nwmzmt'i^wmm 

7.9 Comments 

x? 

t,9 

L 

» 

(Y/N) Ref # Ji_ , Pg # _ 

Ref I ., Pg # 
P.17 

8.0 Transfer Emission Sources Ref # , Pg # . 

8.1 Ar# mmtsif&»?mutti Transferrer / (Y/N) 

8.2 What MterUTs are transferred? 

8.2.1 Product 

8.2.2 Co-Products 

8.3 Comments Ref # , Pg # 
P.18 

9.0 Storage Emission Sources 

9.1 Ar*'(Mtt¥fATt stored? > (Y/N) 

$*? What materials are stored? 

Ref I 

<yS<; ^.e < 

., Pg # 

Storage Service 

Type 

9.2.1 Product 

9.2.2 Co-Products 

/A^^7 sA^* U*klt-J 

T. 

fe 

~7" 

9.2.3 Raw Materials 

qeitQlJeljJyj 

0*ll<t» 7 I^IW-I £ro «./ q ,> / K^r-jMXi 

9.4 Comments 
P.19 

10.0. Wastewater Emission Sources Ref # , Pg # 

10.1 h W&frHto* profett? V (Y/N) 

10.2 Describe wastewater 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

#1 fro- Ht r<*<r^/*tf.'Up'>> M»»« **\faM»/l« ft0

' 

n . i 

#3 ! 

* 

10.3 Stream Composition Ref # , Pg # 

(provide only 1f readily available) 

Stream #1 l 4 " Steam #2 7k; <kfc\ 

Organics Organics 

HAPs HAPs 

Water Water 

Other Other 
Stream #3 

Organics . 

HAPs 

Water 

Other 

P.20 

10.4 Comments Ref # , Pg # 
P.21 

_ 

i 

r 

* 

Preoarer: ^ e^ ' ' "«)><>J> 

Date: s-»7~9o 

Reviewer: 

ADMINISTRATIVE NOTES 

Product-Proc^ codi loZr'+ l 

Hours spent on this PPS '* ^ 

P-P Name A-cet>- ^»M^ f ^'« el<L1J.r<ti'0* ° $ °'«/ ^

 cCc/ 

Incomplete Items (parts of 

form you cannot complete) 

(line # and descrlotlon) Date Cleared Initial s 

c I 

c«->7 > 

fteA' ^T iom-7 /? 

Chemicals missing CAS nmnbers 

n 

Acet:c «c;J tWl 

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

A/^ . SU 1

 a 
P.22 

Preparer:

 /*1twt /*•*'<*oh 

Date: r-/7-9o 

Reviewer: 

Chemical Name 

PRODUCT-PROCESS SUMMARY (PPS) 

fl i-tf.'c 3* l> }drt'Jf 

Alternate Ciffeitor Hm 

tttt t *A ttAfi, Kr v-. ss 

CAS I lo 8^ 7 

Karen Ff«*r 

CHEMICAL SPECIFIC INFORMATION 

t\Cehl ?*."</' 

ooy 

1.0 U.S. Production Ref # ., Pg # ., Ref Year 

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

different reference) 

mmm 

P»|jitiVyons of ko W millions of gallons 

g. 

f 

/^-^^~ y 

i/Kq or S/qallon 

1.8 Comments 
P.23 

2.0 Chemical End-Use Ref # , Pg # , Ref Year 

Use Percent 

f 

I 
3.0 U.S. Producers Ref # 

3.2 Name, Location, and Capacity 

., Pg # ., Ref Year 

million? Of Kg or millions of gallons 

Process Used 

(use P-P #) /nits 

/^7f 

f^-y 

Total Capacity 

iwij.'Ai.^'/^iM-
P.25 

PRODUCT-PROCESS SPECIFIC INFORMATION 

4.0 Potential Product-Processes (P-P) 

Name 

p.p j a,> <z>k:<-(4;o" °/ ^c-el^Cd^ljJt 

MWSf de-kid rn to ow o ^ <\ Ce A e " <•>* d 

Ref I ( z. 

, Pg # 

/</ 

P-P 3 

P-P 4 

P-P 5 

P-P 6 

4.1 Documentation of P-Ps Excluded 

P-P not 

Commercially Viable 

Commercially % Nat'l 

•Viable. (Y/n) Capacity 

y 

/ 

5o {?*?<{J 

r 

Reasons 

cue 

fic ^^'d^Je' /;Q 

d-el-ld^frov. of c ^/, c

 0c/<^ 
P.26 

Air Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Carbonylation Reaction 

Halogenation Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenation Reaction 

Sulfonation Reaction 

Catalytic Reformation 

Hydrodlmerlzatlon Reaction 

Ref i >° . p,iX£L 

oUA?Jr« fr.0\ 

Generic Reactlor 

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

Cc l/W 
P.27 

4.5 Written Description 

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

description. 

Process 

Vapors of glacial acetic acid containing 0.2 to 0.3% triethylphosphate 

(TEP) are passed into a tubular (chrome-iron alloy) reactor heated to 

700 to 800°C under reduced pressure (200 torr). As reaction gases leave 

the converter, ammonia gas (1 kg/4.2 kg TEP) is injected into the 

stream to prevent reversion of the ketene in the product. 

The reactor exit vapors containing acetic anhydride, acetic acid, 

ketene, and water are led to a series of condensers where weak acetic 

acid (30%) is condensed before it can react with the ketene. The uncondensed ketene is absorbed in acetic acid to give acetic anhydride 

(90% purity), which is then fractionated to yield a specification 

product. 

Ketene may also be prepared from acetone according to the equation 

CH.COCH, - CH,=C=0 + CH, 

Acetone vapors are passed through a void chrome-iron tube. The 

temperature of the tube is 650 to 670° C, and the contact time is about 

0.25 to 5 sec. The unchanged acetone is condensed and recycled. The 

gaseous ketene is absorbed in glacial acetic acid to give acetic anhydride. Yields based on acetone are about 80 to 95%. Conversion per 

pass varies from 15 to 25%. 
P.28 

From Acetic Acid (Ketene) 

Cj-Mpt 

Umbamn 

"

SiV¥

"lt 1 

•^-M^^M^M^^r* 

T 

«M am 

i r*fi 

y»,fL?r Co I'Jy-

',:-*. ** \0\ 

5.0 

5.1 

5.2 

Process Flow Diagram (attach at end of package) 

Flow Diagram Reference: Ref I 

Comments on Flow Olagram 

., Pg # '7 

t 

1 

Component TYP « 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

12 ' 7 

Ref # ___ , Pg # 

~ 

6 
P.29 

6.0 Chemical Data 

6.1 Balanced Chemical Reactions Ref # * Pg # ' 

Reaction 

CH8COOH -*• CH2==C=0 + H20 

CH3COOH + CH2=C=0-» (CH3CO)20 

85-89% yield 

6.2 Chemical Tree Ref # . Pg # .J_ 

af-

•f 
P.30 

6.4 Stoichiometry Ref # !^.»x_H 

Show calculations and assumptions and then summarize in table on next 

page. 

lCft7CooH . __v, (c:Hz Col 0 +• Hl Q 

V° > )0^ -f ) % 

w

« 1 € K ^ 0.1% 

18 INDUSTRIAL CHEMICALS 

Material Requirements 

Basis— 1 metric ton acetic anhydride 

Acetic acid 1350 kg 

Catalyst r Small 
rdn ?M 

P.31 

6.4 Stoichiometry Conversion Factors 

a) 

b) 

p-fz-zi 

mm®* for OHPWOMH 

•* t t t tt t t tt t V t t tt t Attt MvttttXiK 

d) {^m^m^m^mti^mmi, 

tti ttt Vt tttt ttW Vtttt SWAWi «V tttttMftAvttt H tttt S t vtttt, JVtttStt V 

e) CMfetfo* 'mttbr 'for C6*mm 

' V. Wt^tttt. t,t •, % t W. *.\ *. S S V V.S IS tf V. \ w 

f) Conversion Factor Comments 

{ts-VU 

3 

i 
P.32 

6.4.1 Product 

acttltL a*.kflro<lt 

6.4.2 Raw Material (s) 

#1 Qce.f:c - a c'J 

n 

#3 

#4 

#5 

6.4.3 Co-Products 

#1 

#2 

#3 

#4 

#5 

6.4.4 Bv-Products 

#1 ^Itft-tli 

#2 

#3 

#4 

#5 

6.4.5 Intermediates 

#1 

#2 

• ItfW 

-

773X18 *5 

1 

/• I % 

-TT 

? 

1 

oAZ 

- - - • 
7.0 Process Vent Emission Sources 

7.1 Arft tltffi process vent emissions? 

tttt. t w t. t f. J5> 

y (Y/N) 

7«2 Air Oxidation vattt eaisslons? ^ (Y/N) Ref # 

o_^ 

ly 

y 

. Pg * J2 

7.3 Comments Ref I ., Pg # 

i l (Y/N) I'L /7 

Ref # J , Pg # 

7.5 Comments Ref I .. Pg # 

P.33 

.zm 
P.34 

sS^J-J 

ML- wmmmm 

7.7 ^WrtBtf 

7,0 

7.9 

Nui^ersot 

Comments 

y,,^Aj[ tP P'< T *' 

dutx <-*l]«v;\t $;~.:L**, VaC<j*n 

f 

Git/** <\ re.z.i/i/'-eJ 

-fy (o^zHlIt 

! 
P.35 

8.0 Transfer Emission Sources Ref # , Pg # 

8.1 tog PTemts/C^Pftfdttcts Transferred! V (Y/N) 

8.2 Mhat materials ire transferred? 

8.2.1 Product 

9.2.2 Co-Products 

8.3 Comments Ref # , Pg # 
P.36 

Q_ $ < </ M*. ^ </ 

9.0 Storage Emission Sources Ref # , Pg # 

9 J toi'MfflUl* stored? / (Y/N) 

$,2 What materials are stored? 

Storage Service 

Name CA||| Type 

9.2 4 Product 

9.2.2 Co-Products 

:'JPL*££ 

i 

I 

9.2.3 Raw Materials 

9.4 Comments 
P.37 

u ltoUf*cJ 

10.0. Wastewater Emission Sources Ref # / ^— . Pg # '7 

••••••••• i y (y/N) 

10.2 Describe wastewater 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

#1 

#2 

#3 

Po„y fU rW/o * / e-V-y/trtror 4i cli^Cafoa . i^\ • i i • r^v* j i » wr . 

! 

10.3 Stream Composition Ref # , Pg # 

(provide only if readily available) 

Stream #1 , 4- Steam #2 

Organics Organics 

HAPs HAPs 

Water Water 

Other Other 
Stream #3 

Organics . 

HAPs 

P.38 

Water 

Other 

f 

I 

10.4 Comments Ref I ., Pg # 
P.39 

ft 

Preparer: . do 

Date: >//7/fo 

Reviewer: 

ADMINISTRATIVE NOTES 

Product-Process Cod* \e*ZH~7 ( 

Hours spent on this PPS 

P-P Name /U/h ^ A^ . /JlnW < Oc / a r/.o/yU^ ^ wKl QU^ 

Incomplete Items (parts of 

form you cannot complete) 

(line # and description) Date Cleared, Initials 

Chemicals missino CAS numbers 

Plant with Citv but no Countv (plant name, city, state) 
Chemical Htm 

CAS /©Saw 7 

PRODUCT-PROCESS SUMMARY (PPS) 

°n*<-yl

 & Nc/* 

J 

CHEMICAL SPECIFIC INFORMATION 

P.40 

Preparer: do 

Date: ifni to 

Reviewer: 

1.0 U.S. Production Ref # .» Pg # ., Ref Year 

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

different reference) 

millions of kg or millions of gallons 

lot)./ 

1.7 Product Price 

S/Ko or i/oallon 

1.8 Comments 
P.41 

2.0 Chemical End-Use Ref # , pg # , Ref Year 

-J** Percmt 

r

^ r *> \°9^* 
3.0 U.S. Producers Ref « ., Pg # ., Ref Year 

millions of Kg fir millions of gallons 

3.2 Naae, Location, and Capacity 

Process Used 

(use P-P I) 

r&C -t* left 7H.7 A 

Total Capacity 
P.43 

rr-PROCESS SPECIFIC INFORMATION 

4.0 potential Product-Processes (P-P) Ref I ., Pg # 

Name 

Cc •W-

 V !,aif 

Comnercially % Nat'1 

Viable (Y/n) Capacity 

oV 

Documentation of P-Ps Excluded 

P-P not 

rciallv Viable Reasons 

JnV iWAyVA^g v\a rc.i4cetJt*.\\<x. oV foeftw/ 

^t-e^^t 
P.44 

lyft^TlreltM* ! Ref f , Pg » 

ir Oxidation Reaction 

Oxidation Reaction 

Alkylation Reaction 

Cajbonylation Reaction^ 

Halogenation Reaction 

Condensation Reaction 

Dehydrogenation Reaction 

Dehydrohalogenation Reaction 

Esterification Reaction 

Hydrogenation Reaction 

Hydrohalogenation Reaction 

Hydroformylation Reaction 

Hydrolysis Reaction 

Nitration Reaction 

Oxyacetylation Reaction 

Oxyhalogenation Reaction 

Sulfonation Reaction 

Catalytic Reformation 

Hydrodlmerlzatlon Reaction 

Generic Reaction 

lain how you selected the reaction type in line 4.3. 

G> <S ^ctckok te £°rr\ 
P.45 

4.5 Written Description 

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

description. 
P.46 

5.0 Process Flow Diagram (attach at end of package) 

5.1 Flow Diagram Reference: Ref # , Pg I 

5.2 Comments on Flow Diagram 

Ref # 

Component Tvoes 

Distillation Columns 

Absorbers 

Strippers 

Reactors 

Condensers 

Vaporizers 

Others 

.. Pg * 

V^i 
P.47 

6.0 Chemical Data 

6.1\ Balanced Chemical Reactions 

CjVi * co 

f ^ V Au-l*** 

Ref I 

., Pg # 

o/\ ^clr^L/ 

6.2 Chemical Tree 

f^e^ l <xte. Ute 

orA^ f^y ^ ^ "^ 

Ref I ., Pg # 

fr^Kc- Ao^y^cl ^ 
P.48 

y 6.4 \sto1ch1ometry Ref I .. Pg # 

Show calculations and assumptions and then summarize in table on next 

page. 

I IS *.*.-•% rS 

m fill 

75,-77 

'/ ' , 

72$ -

tp 

1.S-Y, i$ 

2yy 
P.49 

6.4.1 Product 

6,4,2 Raw Hater1al(s) 

#1 flltWI aci»,Uw? 

#2 C^r^on flfWw",,-l*> 

#3 

#4 

#5 

6.4.3 Co-Products 

#1 

#2 

#3 

#4 

#5 

6.4.4 Bv-Products 

#1 

#2 

#3 

#4 

#5 

6.4.5 Intermediates 

#1 

12 

/o9 :W7 l 
P.50 

6.4 Stoichiometry Conversion Factors 

a) pfoWipor f»> rtopgg \ 

b) c^p^io^Tac^rforCa*Prx)o^J| 

c) cmmm*mmm tammxm 

•.t t -tt tw.tbt tttt tttt t tt AVXV t ttttMy.tM sA .v8 

d) totmnim^MMM:^^>W^M 

w. t Wm w tttttt tttt^t^^t^ttttA-^vt^K^/M^tt^tj^ttyttttttttt tttttt /t V^WCVJCSV^^WM W 

f) Conversion Factor Comments 
P.51 

7.0 Process Vent Emission Sources 

7.1 Arfgffirtfraess vent «ft»i$| ' -J— (Y/N) 

7.2 Air Oxfdaiion vent emissions* (y (Y/N) Ref # ., Pg # 

7.3 Comments Ref I ., Pg # 

i— (Y/N) Ref I ., Pg * 

7.5 Comments Ref I ., Pg # 
P.52 

7JT SflsJ 

7.7 

7'#x'ma&rmF 

7.9 Comments 

$t$Teat!¥3ftH»3 

ni 

1 (Y/N) Ref # , Pg I _ 

Ref # , Pg I 
P.53 

8.0 Transfer Emission Sources Ref # , Pg I 

8 J A*^Spi|&U/<^ $ f (Y/N) 

8.2 What materials are::?r^nsferrtd| 

8.2.1 Product 

ftotKt AnVyr» ^ io 0*1 7 

8.2.2 Co-Products 

8.3 Comments Ref # , Pg # 
P.54 

9.0 Storage Emission Sources Ref # , Pg # 

9.1 Ar* meterfal s stored? Y (Y/N) 

9.2 What materials are stored? 

Storage Service 

9.2.1 Product 

9.2.2 Co-Products 

9.2.3 Raw Materials 

C(.Xhv(\ N\.c\0/xM 

9,2,4 

(Ajkl fLtUh 

7 

. 

Intermediates 

7?2oi v> w \ \ 

9.4 Comments 
P.55 

10.0. Wastewater Emission Sources 

10.2 Describe wastewater 

Ref I ., Pg # 

(Y/N) 

Stream Equipment Component 

Number Producing Wastewater Comments on flow 

#1 

#2 

#3 

10.3 Stream Composition 

(provide only if readily available) 

Stream #1 

Ref I 

Steam 12 

., Pg # 

Organics Organics 

HAPs HAPs 

Water 

Other 

Water 

Other 
P.56 

Stream #3 

Organics _ 

HAPs 

Water 

Other 

10.4 Comments Ref # , Pg # 
P.57 

ID' 

•969 c. ^ ^ 

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 

V 
P.58 

1989 DIRECTORY OF CHEMICAL PRODUCERS 

UNITED STATES PRODUCTS 

Acttic Mi d (Cont'd) 

Hoechst Celanese Corp. 

Hoechst Celanese Chemical Group, 

Inc. 

Quantum Chemical Corp. 

USI Division 

Sterling Chemicals, Inc. 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Solvents and Coatings Materials 

Division 

Clear Lake, Texas 

Pampa, Texas 

Deer Park, Texas 

Texas City, Texas 

Brownsville. Texas 

Taft, Louisiana 

TOTAL 

Annual Capacity 

(Millions of Pounds) 

noo 

550 

620 

590 

700 

40 

4,45 0 

Process and Remarks 

Methanol 

n-Butane LPO 

Methanol carbonylation (low 

pressure) 

Methanol carbonylation (low 

pressure) 

n-Butane LPO; plant is 

mothballed. 

Peracetic acid co-product 

Notes: 

n-Butane LPO » n-Butane liquid phase oxidation 

The following companies recover by-product acetic acid: Air Produas, Hoechst Celanese, Dow, du Pont, Eastman, Monsanto, and Rhone-Poulenc. 

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

Acetic acid amide (See: Acetamide) 

Acetic acid, benzyl ester (See: Benzyl acetate under Flavor 

and Fragrance Chemicals) 

Acetic acid, 2-butoxyethyl ester (See: 2-Butoxyethyl acetate) 

Acetic acid, 4-tert-butylcyclohexyl ester (See: p-tertButylcyclohexyl acetate under Flavor and Fragrance Chemicals) 

Acetic acid, butyl ester (See: n-Butyl acetate) 

Acetic acid, sec-butyl ester (See: sec-Butyl acetate) 

Acetic acid, tert-butyl ester (See: ten-Butyl acetate) 

Acetic acid, dimethylamide (See: N,N-0imethylacetamide) 

Acetic acid, 1-ethenyM,5-dimethyl-4-hexenyl ester 

(See: Linalyl acetate under Flavor and Fragrance Chemicals) 

Acetic acid, 2-ethoxyethyl ester (See: 2-Ethoxyethyl acetate) 

Acetic acid, ethyl ester (See: Ethyl acetate) 

Acetic acid, 2-ethylhexyl ester (See: 2-Ethyl-l -hexyl 

acetate) 

Acetic acid, heptyl ester (See: n-Heptyl acetate under Flavor 

and Fragrance Chemicals) 

Acetic acid, isobutyl ester (See: isobutyl acetate) 

Acetic acid, isopropyl ester (See: isopropyl acetate) 

Acetic acid, methyl ester (See: Methyl acetate) 

Acetic acid, 2-phenethyl ester (See: Phenethyl acetate under 

Flavor and Fragrance Chemicals) 

Acetic acid, 2-phenethyl ester (See: Phenethyl acetate under 

Flavor and Fragrance Chemicals) 

Acetic acid, phenyl ester (See: Phenyl acetate) 

Acetic acid, propyl ester (See: n-Propyl acetate) 

Acetic acid m-tolyl ester (See: m-Cresyi acetate under 

Medicinal (Pharmaceutical) Chemicals) 

Acetic acid, p-tolyl ester (See: p-Tolyl acetate under Flavor 

and Fragrance Chemicals) 

Acetic aldehyde (See: Acetaldehyde) 

Acetic anhydride (Acetyl oxide) 

Eastman Kodak Company 

Eastman Chemical Products, Ine 

Tennessee Eastman Company 

Hoechst Celanese Corp. 

Hoechst Celanese Chemical Group, 

Inc. 

Textile Fibers Group 

Kingsport, Tennessee 

Pampa, Texas 

Narrows, Virginia 

Rock Hill, South Carolina 

Annual Capacity 

(Millions of Pounds) 

700 

500 

300 

250 

250 

Process and Remarks 

Ketene/acetic acid; acetic acid 

from acetaldehyde and recycled 

from cellulose acetate. 

Methyl acetate; carbon monoxide 

from coal-based synthesis gas 

Ketene/acenc aod; acetic acid 

from butane oxidation. 

Ketene/acetic acid; acetic aod 

recycled from cellulose acetate 

Ketene/acetic acid; acetic acid 

recycled from cellulose acetate. 

428 SRI International 

(Continued) 
P.59 

PRODUCTS 

989 DIRECTORY OF CHEMICAL PRODUCERS 

UNITED STATES 

Acetic anhydride (Cont'd) 

Union Carbide Corporation 

Chemicals and Plastics Business 

Group 

Solvents and Coatings Materials 

Division Brownsville, Texas 

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

TOTAL 

Annual Capacity 

(Millions of Pounds) 

250 

2,250 

Process end Remarks 

Acetic acid from butane 

oxidation 

Acetic ether (See: Ethyl acetate) 

Acetidin (See: Ethyl acetate) 

Acetin, tri (See: Triacetin) 

AcetiSOeugenol (See: Isoeugenyl acetate under Flavor and 

Fragrance Chemicals) 

Acetoacetanilide (a-Acetylacetanilide) (/3-Ketobutyranilide) 

Eastman Kodak Company 

Eastman Chemical Produas, inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Hoechst Celanese Corp. 

Specialty Produas Group Coventry, Rhode Island 

Lonza Inc. 

Organic Intermediates Division Bayport, Texas 

Acetoacet-o-anisidide (Acetoacetyi-o-anisidine) 

(Methoxyacetoacetanilide) 

Eastman Kodak Company 

Eastman Chemical Produas, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Hoechst Celanese Corp. 

Specialty Produas Group Coventry, Rhode Island 

Lonza Inc. 

Organic Intermediates Division Bayport, Texas 

Acetoacet-o-chloranilide (o-Acetoacetochloroanilide) (2 -

Chloroacetoacetanilide) 

Hoechst Celanese Corp. 

Specialty Produas Group Coventry, Rhode Island 

Acetoacet-diethylamide (N,N-Diethyl acetoacetamide) 

Lonza Inc. 

Organic Intermediates Division Bayport, Texas 

Acetoacet-2,5-dimethoxy-4-chloroanilide 3-amino-4-

methyl benzamide 

Hoechst Celanese Corp. 

Specialty Produas Group Coventry, Rhode Island 

AcetoacetHJimethylamide (N,N-Dimethylacetoacetamide) 

Eastman Kodak Company 

Eastman Chemical Produas, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Unza Inc. 

Organic Intermediates Division Bayport, Texas 

Acetoacetic acid, ethyl ester (See: Ethyl acetoacetate) 

Acetoacetic acid, methyl ester (See: Methyl acetoacetate) 

Acetoacetic ester (See: Ethyl acetoacetate) 

Acetoacet-monomethylamide 

Unza Inc. 

Organic Intermediates Division Bayport. Texas 

o-Acetoacetochloroanilide (See: Acetoacet-o-chloranilide) 

2',4'-Acetoacetoxylidide (See: Acetoacet-m-xyiidide) 

Acetoacet-sulfanilic acid 

Hoechst Celanese Corp. . 

Specialty Produas Group 

Acetoacet-o-toluidide 

Eastman Kodak Company 

Eastman Chemical Produas, Inc. 

Tennessee Eastman Company 

Hoechst Celanese Corp. 

Specialty Produas Group 

Lonza Inc. 

Organic Intermediates Division 

Acetoacet-m-xylidide (2',4-Acetoacetoxyiidide) 

Eastman Kodak Company 

Eastman Chemical Produas, Inc. 

Tennessee Eastman Company Kingsport, Tennessee 

Hoechst Celanese Corp. 

idr 

Coventry, Rhode Island 

Kingsport, Tennessee 

Coventry, Rhode Island 

Bayport. Texas 

Specialty Produas Group 

Lonza Inc. 

Organic Intermediates Division 

Coventry, Rhode Island 

Bayport, Texas 

Acetoacetyl-o-anisidine (See: Acetoacet-o-amsidide) 

Acetocinnamone (See: 4-Phenyl-3-buten-2-one under Flavor 

and Fragrance Chemicals) 

4-Acetc-3,5-dimethyl-2,6-dinitHMert-butylben*ene 

(See: 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitro-acetophenone 

under Flavor and Fragrance Chemicals) 

Acetoguanamine (2,4-Diamino-6-methyl-s-triazine) (6-

Methyl-1,3,5-triazine-2,4-diamine) 

Dixie Chemical Company Baypon, Texas 

Acetoguanamine-formaldehyde resins (See: Triazone resins 

under Plastics and Resins) 

Acetohexamide (See: Medicinal (Pharmaceutical) Chemicals) 

Acetoin (See: 3-Hydroxy-2-butanone under Flavor and 

Fragrance Chemicals) 

2'-Acetonaphthone (See: Flavor and Fragrance Chemicals) 

/3-Acetonaphthylene (See: 2'-Acetonaphthone under Flavor 

and Fragrance Chemicals) 

Acetone (Dimethyl ketone) (0-Ketopropane) (2-Propanone) 

Allied-Signal Inc. 

Engineered Materials Sector Philadelphia, Pennsylvania 

Annual Capacity 

(Millions of Pounds) 

415 

Process and Remarks 

Cumene peroxidation 

(Continued) 

SRI International 429 
FAITH, KEYES, AND CLARK'S 

INDUSTRIAL 

CHEMICALS 

Fourth Edition 

FREDERICK A. LOWENHEIM 

Plainfield, New Jersey 

Consultant 

MARGUERITE K. MORAN 

Mgr. Technical Information Center, 

M & T Chemicals Inc. Rahway, New Jersey 

A WILEY-INTERSCIENCE PUBLICATION 

JOHN WILEY & SONS 

NewYork Chichester Brisbane Toronto 
ACETIC ANHYDRIDE 

(CH,CO),0 

From Acetaldehyde 

Watir 

Ac»llld«hyd« 

Catalytt 

Qiluent T 

i—L-i Air 

M 

Nitrogen 

Ructor 

Water 

Acetaldehyde 

To 

aldehyde 

column 

Diluent and water 

(—••»« 

J-

 K 

c 

E 

3 

CJ 

U 

T 

*C«tiC 

id 

-Acetic 

anhydrite 

Catalytt 

'•turn 

Reaction 

CH3CHO + Oa -» CH3COOOH 

CH3COOOH + CH3CHO - (CH3CO)20 + HaO 

70-757c yield 

Material Requirements 

Basis—1 metric ton acetic anhydride 

Acetaldehyde 

Catalyst 

Diluent (less recovery) 

Air 

1200 kg 

lkg 

1650 kg 

Variable 

Process 

Air is bubbled through liquid acetaldehyde in a reactor in the 

presence of 2% (based on the weight of acetaldehyde) catalyst, such as a 

mixture of copper and cobalt acetates or manganese acetate, which 

prevents the formation of explosive amounts of peracetic acid. Approximately 1.4 parts of acetic acid per 1 part of acetaldehyde is 

present as a diluent to promote acetic anhydride formation. Methyl or 

ethyl acetate, triacetin, or benzene may also be used as a diluent, and 

16 
P.62 

ACETIC ANHYDRIDE 17 

HDE 

o 3 r Acetic 

acid 

•-Acetic 

anhydride T 

Catalyst 

return 

COOOH 

3CO)20 + H2 0 

the last is generally utilized in conjunction with acetic acid as a 

withdrawing agent in subsequent vacuum distillation to allow separation ofthe reaction mixture from water at lower temperatures. 

The reactor is maintained at a temperature of 50 to 70°C, and the 

pressure is approximately 60 psi (410 kPa). The overheat from the 

crude vacuum column is fractionated in an aldehyde column, yielding 

acetaldehyde for recycle as the overhead and water and diluent as bottoms. The diluent is returned to the reactor after the water is separated. 

The dehydrated mixture of acetic anhydride and acetic acid from the 

bottom of the crude vacuum column is separated by distillation. Acetic 

acid is removed as overhead, and the acetic anhydride is withdrawn 

from a bottom plate. The catalyst is taken from the bottom to be 

reused. The acetic anhydride may be further purified by vacuum distillation. 

Variations of this process involve type and amount of diluent, and 

several stages in the reactor (with oxygen injection into each stage) 

under milder reaction conditions. 

Present trends are away from air and toward oxygen. In one 

continuous process using ethyl acetate as the diluent and a catalyst 

concentration of 1% (cobalt acetate and copper acetate in a weight ratio 

of 2:1), the reaction is carried out at 50°C and 45 psi (310 kPa). 

Oxygen is injected at various points along the path of liquid travel, with 

the overall oxygen supply limited to 1 to 2% excess. Under these conditions. 95% conversions of acetaldehyde are obtained. Both acetic anhydride and acetic acid are produced in a 50:50 weight ratio. 

The same process when carried out in the absence of the diluent gives 

a higher oxidation rate but yields a lower acetic anhydride acetic acid 

ratio (ca. 2:3). 

ihvdride 

1200 kg 

1 kg 

1650 kg 

Variable 

tyde in a reactor in the 

dehyde) catalyst, such as a 

manganese acetate, which 

ints of peracetic acid. Ap1 part of acetaldehyde is 

dride formation. Methyl or 

•o be used as a diluent, and 

From Acetic Acid (Ketene) 

iMbatot 

% * V 

Catalyst 

Vapoiw^l-te«c«ir|.^fconden«r !-».,£ 

F WeatacctK 

aod OOf) 

TJ T 

Tan 

totfc 

Reaction 

CH3COOH -*• CH2=C=0 + H2 0 

CH3COOH + CH 2 =€=0- > (CH3CO)20 

85-897o yield 
18 INDUSTRIAL CHEMICALS 

Material Requirements 

Basis—1 metric ton acetic anhydride 

Acetic acid 1350 kg 

Catalyst Small 

Process 

Vapors of glacial acetic acid containing 0.2 to 0.3% triethylphosphate 

(TEP) are passed into a tubular (chrome-iron alloy) reactor heated to 

700 to 800°C under reduced pressure (200 torr). As reaction gases leave 

the converter, ammonia gas (1 kg/4.2 kg TEP) is injected into the 

stream to prevent reversion ofthe ketene in the product. 

The reactor exit vapors containing acetic anhydride, acetic acid, 

ketene, and water are led to a series of condensers where weak acetic 

acid (30%) is condensed before it can react with the ketene. The uncondensed ketene is absorbed in acetic acid to give acetic anhydride 

(90% purity), which is then fractionated to yield a specification 

product. 

Ketene may also be prepared from acetone according to the equation 

CH,COCH, - CHa=C=0 + CH4 

Acetone vapors are passed through a void chrome-iron tube. The 

temperature of the tube is 650 to 670°C, and the contact time is about 

0.25 to 5 sec. The unchanged acetone is condensed and recycled. The 

gaseous ketene is absorbed in glacial acetic acid to give acetic anhydride. Yields based on acetone are about 80 to 95%. Conversion per 

pass varies from 15 to 25%. 

Use Pattern 

Cellulose esters (including cellulose 

acetate, acetate butyrate, and 

acetate propionate) 

Aspirin 

Miscellaneous 

Percent 

95 

100 
-ALS ACETIC ANHYDRIDE 19 

Production-Acetic Anhydride 

ihydride 

1350 kg 

Small 

2 to 0.3% triethylphosphate 

ron alloy) reactor heated to 

>rr). As reaction gases leave 

TEP) is injected into the 

the product. 

tic anhydride, acetic acid, 

ndensers where weak acetic 

;t with the ketene. The unid to give acetic anhydride 

d to yield a specification 

ie according to the equation 

=0 + CH, 

oid chrome-iron tube. The 

nd the contact time is about 

ondensed and recycled. The 

tic acid to give acetic anhy80 to 95%. Conversion per 

Percent 

95 

100 

2 06 — 

06 

1954 1956 1958 1960 1962 1964 1966 1968 1970 1972 19ri 

P'ice-Acetic Anhydride 

12 .«-

1954 1956 1958 i960 1962 1964 1966 1968 1970 1972 1971 

Miscellaneous 

Properties. Colorless, highly refractive liquid with a strong acetic 

odor. 

Mol. wt 

Spgr 

Weight per gallon 9.01 lb (29°C) 

Soluble in all proportions in ethanol and ether at room temperature. In 

cold water it is soluble to the extent of 13.6 g/100 ml, but decomposes in 

hot water. 

102.09 

1.083 20°C/20 

mp 

bp 

-T3.1°C 

139.9°C 

Flash point (open cup) 

Ignition temperature 

Vapor density (air — 1) 

Explosive limits (% by volume in air) 

Threshold limit value (ppm) 

Grades. Technical (98 and 99%), cp. 

64°C 

390° C 

3.52 

Lower 2.9 

Upper 10.3 

5 
P.65 

f 

20 INDUSTRIAL CHEMICALS 

Containers and Regulations. Aluminum drums and tank cars, 

tank trucks, carboys, and glass bottles. A white DOT shipping label is 

required. 

Economic Aspects 

Acetic anhydride is made in greatest quantity by its chief users, cellulose acetate manufacturers, or by well-integrated organic-chemical 

manufacturers who make a wide variety of related compounds. The two 

manufacturing processes described appear to be competitive. If a manufacturer also produces acetaldehyde for other uses, the acetaldehyde 

oxidation process will probably be preferred. 

For years some acetic anhydride was made from acetylene via 

ethylidene diacetate, but the one plant using the process has been shut 

down. 

Most plants are comparatively large. The smallest has a capacity of 

27 million kg/year, whereas the others vary from 100-million-kg to 385-

million-kg capacity. 

It is reasonable to believe that the future of acetic anhydride manufacture will be closely related to the future of cellulose acetate, hence 

will be governed by gains or losses of the latter in the textile and plastics fields. 

Manufacturers and Plant Sites 

Celanese Corp., Pampa, Texas; Cumberland, Md.; Narrows, Va.; Rock 

Hill, S. C. 

FMC Corp., Meadsville, Pa. 

Tennessee Eastman Co., Kingsport, Tenn. 

Union Carbide Corp., Brownsville. Texas; Texas City, Texas 
Klaus Weissermel 

Hans-Jiirgen Arpe 

Industrial 

Organic Chemistry 

Important 

Raw Materials and 

Intermediates 

Translated by 

Alexander Mullen 

Verlag Chemie • Weinheim • New York 

1978 
P.67 

160 7. Oxidation Products of Ethylene 

3 as chloroacetic acids for organic syntheses 

most important chloroacetic acid: 

CICH;COOH via liquid-phase chlorination 

of CHjCOOH with favored application in 

carhox>meth\lcellulose 

H H 

N

 !_••'' •-' 0 H. M_ / 

CHiOH ' V'

t

' CH,OCH,COOH 

-l. precursor for anhydrides: 

ketene and acetic anhydride 

5 solvent for liquid-phase oxidations 

6. substrate for fermentation to L-lysine or 

L-glutamic acid 

Chloroacetic acids are also important acetic a d 

The most significant of these is monochloroacetj

denVa,iv

«

5

-

world production is estimated to be approx. 180 00n ^ ^ 

ern Europe's share being approx. 120.000 t/a Th ''^"i -

ture of monochloracetic acid results from the chl * m3nn{*-

acetic acid in the liquid phase at approx. 85 T 'na,|°n of 

catalyst but often in the presence of initiators such' 

anhvdride or acetvl chloride. Monochloroacerir ^ J ^ ac<:,lc 

, . ' ' gaeid.as*pn being an important starting material for the manuf 

carboxymethylcellulose. is also an intermediate for "^ °' 

dyes and pharmaceutical preparations. 

' Pesticides. 

Industrially significant secondary products of acetic acid 

are also intermediates (such as acetic anhydride and k 

will be dealt with in the following sections.

 ne| 

Acetic acid is also used as solvent for liquid-phase oxidatio 

for example in the oxidation of p-xylene to terephthalic aad 

dimethyl terephthalate (cf. Section 14.3.2). 

Another application of acetic acid is its fermentation to L-Ks, 

or L-glutamic acid. In the Ajinomoto process, acetic acid serve 

(along with other conventional nutrients) as the main source m 

carbon. If acetic acid is introduced as ammonium acetate then 

nitrogen and carbon are fed to the fermentation by means of 

single carrier. In contrast to the manufacture of D.L-Ksine vtu 

synthetic processes (cf. Sections 10.3.1.4 and 11.3.31. fermentation methods lead directly to L-lysine. Other nutrient sources 

used for L-lysine manufacture are carbohydrates such as maize 

products or molasses. 

acetic acid forms two anhydrides: 

1. intermolecular: 

acetic anhydride (Ac;0) of greater importance, and 

2. intramolecular: 

ketene (diketene) 

Ac.O production (in 10001): 

1974 1975 

USA 741 661 

Japan US 102 

W. Germany 74 54 

n.a. = not available 

1976 

n.a. 

Ill 

66 

Ac.O manufacture via two routes. 

1. oxidative dehydration of CHjCHO 

7.4.2. Acetic Anhydride and Ketene 

Acetic anhydride, the intermolecular, and ketene. the intramolecular, anhydride of acetic acid are very closely related to 

acetic acid as far as manufacture, application and importance 

are concerned. 

The available production figures for anhydride in the most 

important industrial countries are summarized in the adjacent 

table. 

Ketene and its dimer (diketene) are quantitatively of minor 

importance. In 1973 the capacities in W. Germany amountedto 

approx. 20-30.000 t/a. 

There are two different industrial routes for manufactunng 

acetic anhydride. One process type is a modified acetaldehyde 
i 6 8 

MM 

7.4. Secondary Products of Acetaldehyde 161 

cetic acid der,vatlves 

hloroacetic acid TK 

»x. 180.000, a. w "C 

00t

h

a

^manuf a ; 

•J 'Je chl 0 r , nat , 0 n of 

*-

 Cusu a " y without 

tlat0r* such as ace,lc 

•aceticacid. asue ll a s 

r

 the manufacture „f 

'ediate for pesticides. 

s of acetic acid which 

'hydride and ketene) 

s. 

l-phase oxidations, as 

^terephthalic acid or 

nentation to L-lysine 

ess. acetic acid serves 

as the main source of 

ionium acetate, then 

itationbymeansofa 

ure of D.L-lysine via 

Jnd 11.3.3). fermenther nutrient sources 

drates such as maize 

.nidation, whereas the other involves ketene as an intermediate. 

Ihe modified acetaldehyde oxidation was developed by 

Hoechst-Knapsack and a variant by Shawinigan. Instead of Mn 

,cetate a mixture of Cu and Co acetate was used as catalyst. 

The primary acetyl radical, resulting from acetaldehyde by 

abstraction of hydrogen (cf. Acetic Acid by Oxidation of 

Acetaldehyde. Section 7.4.1.1). is oxidized to the acetyl cation 

using Cu:®. which then reacts with acetic acid forming acetic 

anhydride: 

CHjCHO CH,C. 

o -o>» 

CH.C® 

It 

o 

(45) 

CH»C® + CHjCOOH 

II 

O 

CH3C* 

O + Ha 

CH,C 

In a parallel reaction, peracetic acid is formed by addition of 0 : 

to the acetyl radical with subsequent abstraction of hydrogen 

from acetaldehvde. The acid serves to reoxidize Cu® to Cu2®: 

C H 3 C-0-0- H + Cu® - • Cu1® + CHjCO + OHQ 

M 

o 

(46) 

2. dehydration of AcOH via ketene 

m I: 

process principle 

homogeneously catalyzed liquid-phase oxidation of CHjCHO *ith Cu Co acetate 

while forming AcOH as co-product 

process characteristics 

azeotropic H.O removal hinders Ac.O hvdrolysis 

examp^ of process: 

Hoechst-Knapsack 

Shawinigan 

nd ketene. the in-

•ry closely related to 

on and importance 

•dride in the most 

zed in the adjacent 

ntitatively of minor 

rmany amounted to 

for manufacturing 

dified acetaldehvde 

Acetic acid resulting from the acetoxy radical is thus an essential co-product. 

The water formed can now initiate the secondary reaction of 

acetic anhydride to acetic acid if it is not quickly removed from 

the equilibrium by distillation with an entraining agent, e.g. 

ethyl acetate, as in the industrial process. With 95 % conversion 

of acetaldehyde an optimal ratio (56:44) of anhydride to acid is 

attained. 

In the acetic anhydride manufacturing process involving the 

dehydration of acetic acid via ketene (Wacker process), acetic 

acid is initially thermally dissociated into ketene and H20. The 

reaction takes place in the presence of triethyl phosphate at 

700-750°C and reduced pressure: 

to 2: 

principles of two-step process: 

1. catalytically regulated ketene equilibrium, retro-reaction hindered by: 
P.69 

162 7. Oxidation Products of Ethylene 

I. I neutralization of catalyst 

1.2. quenching (lowering of temperature) of 

cracked gases 

CHjCOOH ^ * H,C = C = 0 -f- H,0 (\H - + J? ^ **lmJi. 

(47* 

2. Ac-O manufacture wa non-catalyzed exothermic AcOH addition to ketene 

Finally, the resulting H3PO., is neutralized in the gas phase with 

NH3 or pyridine and the cracked gas is cooled in order to freeze 

the equilibrium. 

The higher boiling accompanying substances (acetic anhvdride 

acetic acid, and water) are separated from the gaseous ketene 

by means of a system of graduated coolers. After removing the 

water, they are recycled to the cracking stage. The ketene 

selectivity reaches almost 90% (based on CH3COOH). The 

ketene purified in this way is directly fed to the acetic acid (e.g 

in the Wacker process) with a liquid ring pump and then converted at 45-55 °C into acetic anhydride: 

H,C = C = 0 + CHjCOOH - (CHjCOkO «fc 

advantages of process: 

1. isolable ketene intermediate 

2. cheap AcOH utilizable e.g. from other 

processes 

3 recovered acetic acid from acetylation 

with Ac.O applicable 

alternative ketene manufacture according to 

principle: 

homogeneously catalvzed demethanaiion of 

(CH.,),CO 

In this stage, selectivity approaches 100%. This acetic mhydride process has the advantage that ketene can be obtained on 

demand as intermediary product. Furthermore, an acetic acid 

feedstock from the most economic process can be employed or 

acetic acid resulting from acetylation reactions with acetic 

anhydride can be reused. 

Besides being synthesized from acetic acid, ketene can also be 

obtained from acetone via thermolysis at 600-700JC in the 

presence of a small amount of CS:: 

CH»COCH, H I H»C-O 0 + CH« 

applications of Ac;0 and ketene: 

1. for acetylation. e.g. AczO for acetyl cellulose, ketene for Ac.O 

A ketene selectivity of 70-80% is attainable with an acetone 

conversion of 25 %. Acetone cracking is only of minor industnal 

importance. A plant is operated by Hofmann La Roche in the 

USA. 

The main application of acetic anhydride is as an acetylating 

agent, above all in the manufacture of acetyl cellulose, as well as 

in the manufacture of pharmaceuticals (e.g. acetylsalicylicacid, 

acetanilide etc.) and of intermediate products. Ketene is also 

employed as an acetylating agent. The special case concerning 

the acetylation of acetic acid to acetic anhydride is the most 

important example. 
P.70 

7.4. Secondary Products of A cetaldehyde 16 3 

(47) 

ized in the gas phase with 

cooled in order to freeze 

anceslaceticanhydride. 

rom the gaseous ketene 

lers. After removing the 

king stage. The ketene 

d on CHjCOOH). The 

d to the acetic acid (e.g. 

ng pump and then conie: 

))jO (48) 

10%. This acetic anhvtene can be obtained on 

hermore. an acetic acid 

ess can be employed or 

reactions with acetic 

cid. ketene can also be 

at 600-700 °C in the 

Ketene is also used in addition reactions (including the dimerization to diketene). 

Diketene is obtained by ketene dimerization in trickle towers. 

into which a liquid stream of the diketene is introduced in 

counter current to ketene at 35-40°C: 

2. for diketene formation 

HjC 

H2COO*=* V l (^--.g^/mol ) (50) 

The reaction virtually goes to completion. Minor amounts of 

ketene are washed out of the off-gas using dilute acetic acid. 

The diketene must be redistilled with particular care since it is 

polymerized by acidic or basic compounds. 

Diketene is an important starting material for the manufacture 

of acetoacetic acid derivatives resulting from the acid or base 

catalyzed addition of alcohols, ammonia, amines, hydrazines, 

etc. 

Acetoacetic acid anilides, with substitution on the phenyl ring, 

find wide application as dye and pharmaceutical intermediates 

just as the pyrazolone derivatives obtained from diketene and 

substituted phenyl hydrazines. 

Vtonomeric ketene forms (3-lactones with aldehydes, e.g. propiolactone is obtained from formaldehyde in the presence of 

A1C1,: 

HCHO + H,C-C O 

lAW.l a. (51) 

diketene also used for manufacture of 

acetoacetic acid derivatives limportant intermediates) 

3. for addition reactions, e.g. 

with HCHO to propiolactone 

with CH,CH = CHCHO to sorbic jc:d 

(49) 

lable with an acetone 

nly of minor industrial 

nann La Roche in the 

ie is as an acetylating 

t\l cellulose, as well as 

.g. acetylsalicylic acid, 

iducts. Ketene is also 

fecial case concerning 

mhydride is the most 

With crotonaldehyde, ketene is converted into a labile P-lactone which can stabilize itself by polyester formation (cf. Sorbic 

Acid, Section 7.4.3). 

7.4.3. Aldol Condensation of Acetaldehyde and Secondary 

Products 

Acetaldehyde, an aldehyde with active a-H atoms, can reaa in 

a characteristic way to form a dimer (acetaldol): 

}CH,CHO •=*-> CH,CH(OHKH,CHO (Stt 

{"--8SH 

acetaldehyde homo-aldolization' to 

0-hydroxybutyraldehyde (acetaldol) 

also co-aldolization' e.g. with HCHO 

to pentaerythritol (cf. Section 8 3 1) 
KE-15+ 

Riegel's 

Handbook of 

Industrial Chemistry 

SEVENTH EDITION 

Edited by 

James A. Kent 

College of Engineering 

Michigan Technological University 

Houghton, Michigan 

VAN NOSTRAND REINHOLD COMPANY 

MIWYORK CINCINNATI ATLANTA DALLAS SAN FRANCISCO 

LONDON TORONTO MIL80URMI 

RADIAN LIBRARr" 

DURHAM, N.C. 
P.72 

SYNTHETIC ORGANIC CHEMICALS 791 

y for the producdride. fl-Butanol, 

thritol combined 

0 per cent of the 

ce the fate of 

by its use as an 

intermediate, fuill have a strong 

is made today 

•, although prothyl alcohol and 

. carried out in 

ycled, and only 

uct. Some acetic 

ion of rc-butane 

i announced for 

lanol and carbon 

, acetaldehyde is 

ssed through the 

0 75 psi. Mangant, is used in the 

on of the explod. Acetaldehyde 

•i with water and 

he liquid reactor 

:nt glacial acetic 

ants use cobalt 

1 as the catalyst, 

mt per pass are 

:r pressures and 

Acetic acid is used chiefly to produce acetic 

anhydride for cellulose acetate manufacture. 

In addition, sizeable quantities are consumed 

in the production of vinyl acetate, acetate esters and salts, and chloroacetic acid. Production of acetic acid was reported as 1.77 billion 

pounds in 1969. 

Acetic Anhydride. Acetic anhydride is produced mainly by processes using acetaldehyde 

and acetic acid with copper and cobalt acetates with some manganese acetate. Concentrations of catalysts are generally 1 to 2 per 

cent. About 1.4 parts of acetic acid per part of 

acetaldehyde are fed to the reactor system. 

The reactor is run at 50-70 per cent and about 

60 psi. Finishing is done in a vacuum distillation train. 

In some newer processes oxygen replaces air 

as the oxidizing agent. The reaction is carried 

out at lower temperatures and pressures. 

Higher (95 per cent) conversions of acetaldehyde are obtained, and acetic anhydride and 

acetic acid are produced in a 50:50 weight 

ratio. Running the same process in the absence 

of diluent gives a higher oxidation rate but a 

lower (2:3) anhydride-acid ratio. 

Of the 1.68 billion pounds of acetic anhydride reported produced in 1969, some 85 per 

cent probably was used to make cellulose acetates, about 10 per cent for vinyl acetate, and 

5 per cent for aspirin and other esterification 

reactions. 

Vinyl Acetate. Of some 729 million pounds 

produced in 1969, less than 100 million were 

produced by the new oxyacetylation process 

(using ethylene, acetic acid, and oxygen). The 

new process yields acetaldehyde as a by-product in adequate quantity to be converted to 

the acetic acid needed. This means that the 

only net feed to the complex is ethylene. 

At present, some 600 million pounds of 

vinyl acetate capacity exist. It is apparent that 

this is another case where acetylene is rapidly 

being replaced. A flow diagram for the oxyacetylation process is shown in Fig. 25.14. 

Ethylene Oligomers 

Linear primary alcohols and ct-olefins in the 

C6 to C10 range and the C12 to C18 range have 

become important industrial chemicals in recent years. The linear alcohols in the C6 to 

C10 range are used to make plasticizers for 

Processing. 50, No. Fig. 25.14 Vinyl acetate by oxyacetylation process. [Hydrocarbon Processing, 50, No. 11, 219 (1971); copyright 1971 by Gulf Publishing Co. I 
P.73 

IEST 

PHYSICS HANDBOOK 

K FOR MECHANICAL 

RING CALCULATIONS 

\NDBOOK 

> RESINS 

AL ENCINEERS 

)BOOK 

;ULATIONS 

Y 

vTION METHODS 

ESSES 

DBOOK 

R FUNDAMENTALS 

R APPLICATIONS 

• GINEERING 

< FOR CHEMICAL 

HANDBOOK OF 

CHEMICALS 

PRODUCTION 

PROCESSES 

ROBERT A. MEYERS 

EDITOR IN CHIEF 

CHEMICAL PROCESS TECHNOLOGY HANDBOOK SERIES 

OGY 

McGRAW-HILL BOOK COMPANY 

New York St. Louis San Francisco Auckland 

Bogota Hamburg Johannesburg London Madrid 

Mexico Montreal New Delhi Panama Paris 

Slo Paulo Singapore Sydney Tokyo Toronto 
P.74 

Ll 

Halcon SD Group Acetic 

Anhydride Process 

B. Juran 

Halcon SD Group, New York, New York 

Introduction 

Perspective 

Process Description andChemistry 

Yields 

Product Specifications 

Wastes and Emissions 

Economics 

References 

1-4 

1-4 

1-4 

1-6 

1-6 

1-7 

1-7 

1-9 

1.13 
1.1-4 ORGANIC CHEMICALS 

INTRODUCTION 

A new process to manufacture acetic anhydride was commercialized during IQB.. 

This route starts with methanol and carbon monoxide, and does not pr0c 

through acetic acid or acetaldehyde as do older technologies. It thus represen 

significant advance for C, chemistry, defined as the synthesis of higher-number ' 

bon molecules from single-carbon feedstocks. 

Acetic anhvdride is produced from C, materials by Tennessee Eastman Co 

panv, a division of Eastman Kodak, using technology jointlv developed bv Eastm 

and the Halcon SD Group. Capacity of the plant, located at Kingsport, Tenness 

is 500 million lb/yr (227,000 Mg/yr), making it the world's largest acetic anhvdriri 

facility. Eastman produces synthesis gas for methanol manufacture and CO forth 

carbonylation reaction by gasifying coal. 

PERSPECTIVE 

Acetic anhydride is a mature intermediate chemical, whose domestic 1984 produc 

tion was about 1 billion lb (454,000 Mg). All current U.S. production is based on 

acetic acid cracking to ketene, which is further reacted with additional acid to vieM 

the anhydride. Some companies in Europe still oxidize acetaldehvde to anhvdride 

although the economics of this process are less favorable than the ketene route 

The major end products of acetic anhydride are cellulose acetate fibers and plaj. 

tics. Most of the fiber material is used for cigarette filters, while a lesser amount n 

used to produce fabrics for the apparel industry and the home. A small quantity..r 

acetic anhydride is used in the manufacture of pharmaceuticals and plasticizers 

and to make the explosive, cyclonite. 

With relatively mature processes and a slowly growing market, it might seem 

there would be little incentive to develop new technology for the production ,,\ 

acetic anhydride. However, the rapid surge in energy and feedstock costs dunnj 

the 1970s provided an impetus to search for routes to intermediates that consumed 

less energy per unit of product and that relied on more secure, and more witielv 

available, feedstocks than those based on oil. 

In 1980, Halcon SD and Tennessee Eastman announced just such a process for 

acetic anhydride. It is based on methanol and CO, materials that can be made from 

a wide variety of feedstocks ranging from natural gas to naphtha, residual oil. coal, 

lignite, and oil shale—i.e., any hydrocarbon material that can be gasified. Moreover, utility costs per unit of product are far less for this new C,-based technology. 

Eastman's decision to utilize the carbonylation route to acetic anhvdride represented a switch to lower-production-cost technology and a more secure and abundant feedstock, coal. 

PROCESS DESCRIPTION AND CHEMISTRY 

The carbonylation process for acetic anhydride involves two steps, and the flowsheet will look slightly different depending on whether recycle acetic acid is avail-
P.76 

A1.S 

o was commercialized during 1983. 

monoxide, and does not proceed 

r technologies. It thus represents a 

the synthesis of higher-number carcrials b% Tennessee Eastman Comulogy jointly developed bv Eastman 

it. located at Kingsport. Tennessee, 

die world's largest acetic anhvdride 

hanol manufacture and (!(') for the 

lical, whose domestic 1984 producarrent L'.S. production is based on 

-eacted with additional acid to vield 

oxidize acetaldehvde to anhvdride, 

favorable than the ketene route, 

arc cellulose acetate fibers and plasette filters, while a lesser amount is 

. and the home. A small quantity of 

f pharmaceuticals and plasticizers. 

\lv growing market, it might seem 

technology for the production of 

energy and feedstock costs during 

.tes to intermediates that consumed 

on more secure, and more widelv 

: announced just such a process for 

O. materials that can be made from 

al gas to naphtha, residual oil. coal, 

aterial that can be gasified. More-

- for this new C,-based technology, 

route to acetic anhvdride repre-

!ogv and a more secure and abun-

>TRY 

.• invokes two steps, and the HowAliether recycle acetic acid is availHALCON SD CROUP ACETIC ANHVDRIDE PROCESS 1.1-5 

hie. (Recycle acid is derived from the production of cellulose acetate when acetic 

nhvdride is reacted with cellulose, or from other commercial acetvlation 

processes.) 

When recvele acetic acid is not readily available, acetic anhvdride is made from 

uethanol and CO onlv. as shown in Fig. 1.1-1. Two mol of methvl acetate are carherniated with 2 mol of CO to give 2 mol of anhvdride. Half the anhvdride is 

removed as product, while the other half is recycled and reacted with methanol to 

(rive 2 mol of methvl acetate and 1 mol of water. Thus the overall reaction is methanol plus CO to vield acetic anhydride and water, the water always being removed. 

Ihe methanol, of course, is made from CO and hvdrogen. so acetic anhsdride 

derived entirely from synthesis gas is the result. 

When recvele acetic acid is available, however, as is the case for Eastman's operations, the process follows the chemical route shown in Fig. 1.1-2. Methanol is 

esterified with the acetic acid to vield methvl acetate and water. In the same manner 

as previously, the water is removed and the methvl acetate is carbonvlated to form 

acetic anhydride. 

The block process flowsheet for producing acetic anhydride from methanol and 

QO. without an external supply of acetic acid, is shown in Fig. 1.1-3. Methvl acetate 

Is formed by means of a novel and efficient system. The ester is made at nearly 

quantitative yields, while considerably less capital and energy- are required compared with classical esterification technologies. Sulfuric acid at low concentrations 

is used as a catalvst. The reaction is carried out in a tower reactor at essentially li>0 

percent conversion and selectivity, and purified methvl acetate is recovered as a 

distillate product. 

In the carbonylation section, methvl acetate and carbon monoxide combine to 

form acetic anhvdride. A multicomponent. homogeneous cataUtic svstem permits 

the reaction to proceed under moderate conditions of temperature and pressure. 

2MeOAc 

AcjO 

2C0 

2MeOH 

2AcjO 

ZMeOAc NjO 

2MeOH 2C0 AcjO Ma0 (Net I 

FIG. 1.1-1 Chemistry of acetic anhvdride production when no 

recycle acetic acid is available. MeOAc • methylacetate; Ac20 

=. acetic anhvdride; MeOH - methanol. 

MeOH 

MeOAc 

HOAc 

CO 

MeOAc 

ACzO 

MjO 

MeOH HOAc CO Ac20 H 2 0 (Net) 

FIG. 1.1-2 Chemistry of acetic anhydride production with the 

use of available acetic acid. HOAc • acetic acid. 
1.1-6 

CarDon mononde 

ORGANIC CHEMICALS 

• 

Metnanoi Esterification 

Methyl aceiote 

o 

1 

iat ion | 

• I 

Water 

Recycle acetic anhydride 

P-jr.fication 

•ice' 

i-"' it 

FIG. 1.1-3 Schematic (lowsheet of acetic anhvdride production. 

Reactor effluent is reduced in pressure and fed to the purification section 

Acetic anhydride is separated from light and heavy impurities bv conventional distillation; the product meets the most rigid industry specifications. 

YIELDS __ _ 

Reactor and distillation yields throughout the process are very high. The estenti. 

cation of methanol to methyl acetate proceeds nearly quantitatively, and the \i<ia 

for this section is over 99.9 percent. Selectivity of carbonvlating methvl acetate t,, 

acetic anhydride is well above 95 percent, as is the overall vield from methanol :., 

product anhydride. 

High-purity carbon monoxide is not required for the carbonylation reaction, 

and a cheaper CO feed with several percent hydrogen or other inerts in it is accentable and even preferred in terms of cost. The vield on CO depends pnmar.K sn 

the inerts level in the feed gas, but typically will be about 90 percent. 

v 

PRODUCT SPECIFICATIONS 

High-purity acetic anhydride is produced by the distillation of the reactor effluent. 

Typical sales specifications are as follows: 

Acetic anhydride 

Specific gravity 

Color (Pt.-Co. scale) 

Reducing substances 

99.0 wt % (min.) 

1.080 to 1.085 

5 max. 

Pink color shall be retained for at least 5 min when 

0.1 mL of 0.LV KMnO, is added to 2-mL sample 

Acetic acid makes up essentially all the remaining 1 percent of the product. 
P.78 

IEMICALS 

j | 

' 

nde 

ndrid c produ c 

< 

/lotion | 

' 

cation 

ion . 

Acetic 

OrOOuCI 

HALCON SD CROUP ACETIC ANHYDRIDE PROCESS 1.1-7 

ire and fed to the purification section, 

md heavy impurities bv conventional disI industry specifications. 

t the process are very high. The esterifi-

;eeds nearly quantitatively, and the vield 

.tivitv of carbonviating methvl acetate to 

. as is the overall yield from methanol to 

equired for the carbonvlation reaction, 

it hvdrogen or other inerts in it is acceptThe yield on CO depends primarily on 

ily will be about 90 percent. 

bv the distillation of the reactor effluent. 

nin.) 

85 

hall be retained for at least 5 min when 

•AN KMnO, is added to 2-mL sample 

maining 1 percent of the product. 

^CTE S AND EMISSIONS 

The carbonvlation process for acetic anhydride from methanol and CO results in 

h e formation of three waste streams: vented gases, water of esterification, and 

l,eavv organics. 

Inert gases entering with the carbon monoxide feed must be purged. This vent 

stream contains CO as well, and is thoroughly treated in a series of scrubbers to 

recover essentially all organic materials before discharge. It is sent to a boiler or 

oCess furnace for combustion of the CO (and any hydrogen that mav be present). 

Esterification of methanol yields 1 mol of water per mole of methvl acetate 

tbrnied. This aqueous waste stream is sufficiently stripped of organics in the esterhe ation section that its disposal does not pose any problem. Tvpicallv. it could be 

•onibined with other plant aqueous wastes for either biotreatment or direct disnosal. depending on local conditions. 

The small quantities of heaw organic compounds formed in the reaction section 

and in the distillation equipment are disposed of bv incineration. 

ECONOMICS 

The estimated battery limits capital cost for a plant to produce 500 million lb vr 

(•J2T.000 Mg/yr) of acetic anhydride by the Halcon/ Eastman carbonvlation process 

Is $63 million, as shown in Table l.l-l. 

Assumed in making this estimate are L'.S. Gulf Coast construction, a first-quarter 1983 cost basis, and no import of recycle acid into the plant (i.e., all acetyls 

generated within the process use only methanol and CO feedstocks). 

Operating requirements are also given in Table l.l-l. About 0.66 weight of 

methanol and 0.62 weight of CO are required per weight of acetic anhvdride produced. Steam is used at the rate of 1.6 lb/lb anhydride. 

A set of unit prices has been assumed so that acetic anhvdride production costs 

can be calculated. These unit prices for feedstocks and utilities are given in Table 

TABLE 1.1-1 Operating Requirements for Manufactunng 500 Million lb 

(227,000 Mg/yr) of Acetic Anhydride by the Carbonvlation Process 

Battery limits capital cost* 

Annual operating requirements 

Methanol 

Carbon monoxide 

Catalvsts and chemicals (cost) 

Steam 

Electric power 

Cooling water circulationt 

Fuel credit 

$63 million 

3.28 X 10fi lb (1.48 X 10* kg) 

3.09 X 10° lb (1.40 X 10" kg) 

$1.0 million 

7.95 X IO6 lb (3.60 X 106 kg) 

1.4 X 10'kWh(5X 10: MJ) 

1.2 X 1010 gal (4.5 X 1010 L) 

1.6 X 10" Btu (1.7 X 10" kj) 

•Basis: U.S. Gulf Coast, first-quarter 1983. 

t7'C rise. 
P.79 

1.1-8 ORGANIC CHEMICALS 

1.1-2, and are indicative of early 1983 costs. CO at $0.04 per pound ($0,088 per 

kilogram) is based on synthesis gas generation on a large scale—larger than the 

quantity needed solely for acetic anhydride production. This could be done, for 

example, bv including methanol manufacture as well in a coal-to-chemicals complex. Alternatively, methanol and CO could be purchased from large-scale producers, who currently use natural gas but will be using a varietv of carbon sources in 

the future. 

L'sing the operating requirements and unit costs shown in Tables 1.1-1 and 1.1-

2. the production cost for acetic anhvdride can be calculated. This information is 

summarized in Table 1.1-3, which presents simplified economics using a 10 percent 

depreciation rate and a 20 percent return on investment. The production cost of. 

SO. 18 per pound of anhvdride (SO.40 per kilogTam) is considerably below the late 

1982 selling price of about $0.30 per pound ($0.66 per kilogram), and the process 

thus offers a significant advantage over a new plant that would produce acetic acid 

first, then anhvdride via ketene. 

TABLE 1.1-2 Init Costs 

Methanol 

Carbon monoxide 

Steam (medium pressure) 

Electric power 

Cooling water 

$0.60/gal ($0.20 kg) 

$0.04/lbi$0.088'kg) 

$6/thousand lb iSO.0132. kg) 

$0.04/kVVh (SO.01 ll.MJ) 

$0.10,'thousand gal ($0.0265 m') 

TABLE 1.1-3 Economics of Producing 500 Million lb/yr (227.000 Mg, vn of Aceti. 

Anhvdride 

Capital costs 

Battery limits capital cost 

Offsites 

Total fixed capital 

Production costs 

Raw materials 

Utilities 

Fixed costs 

Depreciation, @ 10%/yr 

Return, @ 20%/yr 

Ceneral and administrative, sales, research 

Product value 

$63 million 

$25 million 

$88 million 

Mb Anhydride t, kg Anhvdride 

8.6 

1.2 

1.8 

1.8 

3.6 

1.3 

18.3 

18.9 

2.T 

4.0 

4.0 

7.9 

2.9 

40.3 
An Introduction to 

INDUSTRIAL ORGANIC 

CHEMISTRY 

Second Edition 

PETER WISEMAN 

Department of Chemistry 

University of Manchester Institute of Science and Technology 

APPLIED SCIENCE PUBLISHERS LTD 

LONDON 
P.81 

•V TO INDUSTRIAL ORGANIC CHEMISTRY 

leroxide. peracetic acid: 

CH,C- 4- XH 

0 

II 

CHjCOO0 

II 

CH,C- + 

0 

•I 

CH,COOH 

peracetic 

acid 

les, peracetic acid cleaves readily across 

to give fragments that can participate in 

OXIDATION 103 

The oxidation is normally carried out with air, at temperatures 

in the range 60 to 80 °C. manganese or cobalt acetate being used 

as the catalyst. Yields of about 95% are obtained, the main loss 

being through beta -scission of acetoxy radicals: 

O 

II 

CHjCOCO, CH, CO, + H,0 + other products 

If the oxidation is carried out in the presence of a mixture of 

cobalt and copper acetates, a mixture of acetic acid and acetic 

anhydride is obtained: 

CH,C- 4- Cu2' CH,C 4- Cu+ 

CH,CO- + HOO O 

CH,C- 4- CH,COH 

ot to be the main route by which acetic 

the peracetic acid reacts with acetaldethyl peracetate. which then decomposes 

i free radicals, to acetic acid: 

>

c

x — CH >

c

; 

H H 

OH O 

- H 

OH O 

I II 

1 ^CHjC — OOCCH, •CH.COOCCH, 

I I 3 ' I ' 

H H H 

* - hydroxyethyl 

peracetate 

-CH, :CH,CO,H 

CH,C 4- CHjCOH 

CH,COOH 4- Cu* 

// CH,C 

\ 

,0 + H' / 

CH,C 

O 

CH,CO- 4- Cu:* 4- OH 

This is the basis for one of the commercial processes for the 

manufacture of acetic anhydride. It is also made from acetic acid 

shown below: 

700-800 °C CH,CO,H , • ., , • ,—' CH,=C=0 •»• H,0 ^"'^

 2 methyl phosphate 

(catalyst) <«'<"« 

CHj=0=0 + CHjCOOH 

CHjC 

O 

CH,C 

/ 

V 
104 INTRODUCTION TO INDUSTRIAL ORGANIC CHEMISTRY 

The main uses of acetic acid and acetic anhydride are in the 

manufacture of acetates, of which cellulose acetate (Section 8.11) 

and vinyl acetate (Sections 5.12 and 5.16) are the most important. 

As we will see later in this chapter, acetaldehyde-based routes 

to acetic acid and acetic anhydride are coming under increasing 

competition from other routes. 

5.4 Oxidation of Cyclohexane 

The hydrogens of cyclohexane are much more difficult to remove 

than the aldehydic hydrogen of acetaldehyde. or the tertiary 

hydrogen of cumene, and more severe conditions are required for 

its oxidation than in the cases of these compounds. Partly as a 

consequence of this and the fact that the products are more 

readily oxidised than the cyclohexane itself, the chemistry involved is much more complex than in the two previous cases. 

The oxidation of cyclohexane can give rise to a large number of 

products. It is carried out commercially on a very large scale for 

the manufacture of cyclohexanol/cyclohexanone mixtures ('mixed 

oils'), which are intermediates in nylon manufacture. The reaction follows the typical steps up to the formation of the hydroperoxide. (Note: for the sake of simplicity, only those hydrogen 

atoms which are involved in the reaction are shown in the 

following reaction schemes.) 

+ X 

4-0, 

- XH 

H\.00 -

+ C4H12 
P.83 

IO>W-#0 

KIRK-OTHMER 

CONCISE ENCYCLOPEDIA 

OF CHEMICAL TECHNOLOGY 

PLEASE DO NOT 

REMOVE FROM 

LIBRARY 

RADIAN LIBRARY 

RESEARCH TRIANGLE PARK. NC A WILEY-INTERSCIENCE PUBLICATION 

John Wiley & Sons 

NEWYORK • CHICHESTER • BRISBANE • TORONTO • SINGAPORE 
P.84 

10 ACETIC ACID AND DERIVATIVES 

Health and Safety Factors 

Any solution containing more than half acetic acid in water or organic 

solvents is considered corrosive. These solutions cause damage to skin, 

eyes, nose, and mouth. There is no burning sensation upon application to 

unbroken skin, although symptoms appear as blisters within 30 min to 4 

h. There is little or no pain experienced, unless sensory nerve receptors 

are attacked. Medical care should be sought immediately. Particular care 

is needed when handling acetic acid to avoid spilling it on the skin or 

clothing and to avoid breathing the vapors. When exposed, wash acetic 

acid away with large amounts of water or dilute sodium bicarbonate 

solution. Washing blisters that have already appeared will not alleviate 

the pain. Leave areas where the odor of acetic acid vapors is noticeable. 

Glacial acetic acid causes severe gastric difficulties if swallowed, but 

the precise toxic dose for humans is not known. OSHA standard for air 

in work places is a time-weighted average of 10 ppm. 

FRANK S. WAGNER, JR. 

Celanese Chemical Company 

A.I. Popov in J.J. Lagowski, ed., The Chemistry of Nonaqueous Solvents, Vol. 

3, Academic Press, Inc.. New York, 1966-1976, Chapt. 5. 

ACETAMIDE 

Acetamide, CH3CONH2 , mol wt 59.07, is a colorless, deliquescent 

substance composed of rhombohedral crystals. Also known as acetic acid 

amide, ethanamide, and methane-carboxamide, it is odorless when pure; 

otherwise, it has a distinctive odor due to an unknown impurity. It is an 

excellent dipolar solvent for organic and inorganic compounds; it is 

compatible with hydrocarbons, ketones, esters, organic acids, alcohols, 

water, ammonium salts, and ammonia and its derivatives. Its high 

dielectric constant (f = 59) makes it a suitable solvent for inorganic 

compounds. 

Physical and Chemical Properties 

Acetamide has mp 81.0°C, bp 221.2°C, n

:

D

8J 1.4274, d|£ 1.159 g/cm3

, 

and vapor pressure (at 105°Cl 1.33 kPa (10 mm Hg). It is chemically 

neutral in the classical sense but basic enough to accept a proton from a 

strong acid. It reacts with alkali metals to give the corresponding metal 

derivatives, eg, CH3CONHNa. It is useful in the bromination of acidsensitive compounds since it forms a stable complex with hydrogen 

bromide (CH3CONH2 )•_,. HBr which is insoluble in common bromination 

solvents. Acetamide is dehydrated to acetonitrile when heated either 

with phosphorus pentoxide or acetic anhydride. It is saponified by hot 

alkali and hydrolyzed by hot acid. It can be converted to acetic acid byheating with mineral acids and by reaction with nitrous acid. 

Preparation 

One of the most widely used methods of manufacture is classical 

svnthesis from acetic acid and ammonium carbonate: 

CH,C(0)OH 

(NH,),CO, 

CH,C(0)ONH4 - •CHXONH., - HOH 

cloth, films, and coatings; as a humectant for paper; as a stabilizer in 

peroxides; as a raw material in organic synthesis; and in the preparation 

of hypnotics, insecticides, and a variety of plastics. 

THERESA A. MORETTI 

American Hoechst Corporation 

J. Zabicky, The Chemistry ol Amides, Interscience Publishers, a division of 

John Wiley & Sons. Inc., New York, 1970. 

ACETIC ANHYDRIDE 

Acetic anhydride, (CH3CO)50 (often abbreviated Ac20), is a mobile, 

colorless liquid with a penetrating, choking odor, closely related to acetic 

acid. It is the largest commercially produced acid anhydride; current 

U.S. production ranges from 500 to 750 thousand metric tons annually. 

It is used in industry for acetylation reactions and as a solvent in 

laboratory applications. The greatest single application is in the manufacture of cellulose esters, chiefly cellulose acetate (see Cellulose acetate 

and triacetate fibers; Cellulose derivatives, esters). It is also used in 

starch acetylation to make textile sizing agents, in salicylic acid acetylation to aspirin (see Salicylic acid and related compounds), and in electrolytic polishing of metals, especially aluminum, and semiconductor 

processing. An undetermined quantity goes into the manufacture of 

chloroacetic acid (see Acetic acid, halogenated derivatives) and acetyl 

chloride (qv). It is peculiarly useful for oxidation reactions, not only of 

metals but also for organic compounds. 

Physical and Chemical Properties 

The physical properties of acetic anhydride are given in Table 1. 

The chief impurity in acetic anhydride is acetic acid, which is troublesome to remove completely. Purity of the product is best gauged by the 

refractive index or the specific conductivity. Traces of acetic acid are 

detected by near-ir spectroscopy. Acetic acid can be estimated by difference when the anhydride is assayed with aniline. 

Thermal decomposition of acetic anhydride yields ketene. in a unimolecular dissociation process between 280 and 650°C, making this a 

convenient way to prepare ketene in the laboratory (see Ketenes and 

related substances). Photolysis of acetic anhydride generates ethane and 

carbon monoxide in approximately equal amounts, and carbon dioxide in 

smaller quantities. Acetic anhydride appears to ionize to acetylium and 

acetate ions although it is practically an electrical insulator when salt 

free. The acetylium ion, CH3CO*. occurs in strongly acid solutions. 

Potassium acetate, rubidium acetate, and cesium acetate are very soluble 

in acetic anhydride, but sodium acetate is only slightly soluble. Barium 

acetate is the only soluble alkaline-earth acetate. Heavy-metal acetates 

are poorly soluble. 

Table 1. Physical Properties of Acetic Anhydride 

Widely used laboratory methods are 

CH3COCl - 2 NH., - CH3CONH2 - NH4CI 

(CH3CO) 2 0 - 2 NH:) - CH3CONH2 + CH3COONH4 

CH3COOC2H5 - NH3 - CH3CONH2 + C2H,5OH 

The most efficient method is distillation of ammonium acetate. 

Acetamide is produced in technical and reagent grades, the latter 

obtained by further recrystallization. Acetamide is shipped in fiber 

cartons and in 500-g packages, and should be stored in a cool, dry area. 

It is analyzed by hydrolysis to the acid, or by esterification. 

Acetamide is used as general solvent and in the textile industry; it also 

has applications as an accelerator in the estimation of bilirubin; as an 

antidote against monofluoroacetamide poisoning; as an antacid in the 

lacquer, explosives, and cosmetic industries; as a plasticizer in leather, 

Property 

melting point. °C 

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

vapor pressure equation. kPa (A - 6.2">14) 

(mm Hg (A - 7.1265) 

thermal conductivity, liquid. mW . im Ki. at tO'C 

specific heat, J/kg" . at 20°C 

heat of vaporization at bp. •].'%" 

density, df. g/cm' 

refractive index, nj 1 

surface tension. mN /m ( - dvn -cm), at 20CC 

viscosity. mPa s ( - cP), at 20°C 

dielectric constant, f2" 

dipole moment, C m6 

Va 

-7-4.1.1 

138.6.1 

log p = A 

136 

1817 

4(»i.« 

1.0820 

1..W92 

:IJ.6.r> 

0.901 

22.1 

9.:l » 10 

lue 

1-127.8 

{IH* - t) 

"To convert J to cal, divide by 4.184. 

"To convert C m to debve, divide by 3.336 x 10 ''*>. 
ACETIC ACID AND DERIVATIVES 11 

Acetaldehyde adds to acetic anhydride to furnish ethylidene diacetate, 

CH3CH(02CCH3)2. The higher carboxylic acid anhydrides may be prepared conveniently by a double decomposition reaction with acetic 

anhydride and the higher acid. Since acetic acid boils lower than the 

other fatty acids, it can be distilled and the higher acid anhydride 

recovered. 

Manufacture 

There are three main routes to acetic anhydride that are thoroughly 

understood from an engineering standpoint; the processes depend fundamentally upon their distinctive raw materials, ie, acetic acid, acetone, 

and acetaldehyde, for anhydride manufacture. 

The acetic acid process involves the endothermic decomposition of 

acetic acid to ketene and the addition of ketene to acetic acid in the 

liquid phase to produce acetic anhydride. 

CH.,C(0)OH + CH 2 =C=0 -

(CH3CO)20 +62.8 kJ/mol (15 kcal/mol) 

The acetone process involves a similar thermal decomposition of 

acetone to ketene in a reaction that is less endothermic. Pyrolysis gases 

are quenched in a liquid recycle mixture composed of acetic acid and 

anhydride; the quenched gases consist of ketene, acetic acid, acetic 

anhydride, unconverted acetone, and the permanent gases. During condensation, practically all the ketene reacts with acetic acid to form acetic 

anhydride. Three distillations recover the acetone, a mixture of acetic 

acid and anhydride (which is used for quenching), and pure acetic 

anhydride. 

Liquid-phase acetaldehyde oxidation yields acetic acid (as a by-product) and acetaldehyde monoperacetate, which decomposes into acetic 

anhydride and water. The product may be removed as a liquid or a 

vapor; as a vapor, the concentration of acetic anhydride is higher than 

that of acetic acid; air is used to entrain the acetic anhydride and water 

as fast as they are made. Purification of the liquid products is comparatively easy; low boiling substances are removed with ethyl acetate or 

acetic acid before the anhydride is distilled. 

A number of other routes to acetic anhydride manufacture investigated include methyl acetate, a by-product of methanol carbonylation 

(see Acetic acid), pyrolyzed to ketene in a system similar to that used for 

acetone or carbonylated to acetic anhydride in the presence of metal 

catalyst; and sodium acetate and carbon dioxide reactions form sodium 

bicarbonate and acetic anhydride in aqueous solutions. 

Health and Safety Factors 

Acetic anhydride has a powerful effect on the human body. The odor 

threshold is 0.49 mg/m3. and the eyes are affected by as little as 0.36 

mg/m1. Concentrations > 0.03 mg/m3 throughout a regular workday 

are inadvisable. Acetic anhydride penetrates the skin quickly and can 

form painful burns and blisters that are slow to heal, lt is particularly 

dangerous to the tissues of the eyes, nose, and mouth; rubber gloves, 

masks, and goggles are recommended. 

FRANKS. WAGNER, JR. 

Celanese Chemical Company 

GV. Jeffreys. The Manufacture of Acetic Anhydride. 2nd ed.. the Institution 

of Chemical Engineers. London, 1964. 

ACETYL CHLORIDE 

Acetyl chloride (ethanoyl chloride), CH3C0C1, is a colorless, mobile 

liquid with a pungent odor. It fumes in moist air, and its vapors are 

extremely irritating to the eyes, nose, and throat. 

Acetyl chloride is used as a catalyst in the chlorination of acetic acid; 

for this use it is made in situ from acetic anhydride and by-product 

hydrogen chloride. It is used as a powerful acetylating agent in organic 

synthesis, particularly with a Lewis acid catalyst; it will acetylate many 

compounds, eg, benzene, that cannot be acetylated with acetic acid or 

acetic anhydride. Acetyl chloride is used to synthesize pharmaceuticals 

and dyes; in the preparation of acetanilide, acetophenone, and other 

acetyl derivatives; and in the laboratory to determine hydroxyl groups; 

in qualitative organic analyses for distinguishing tertiary from primary 

and secondary amines. It is also used to form phenolic compound 

derivatives; as a chlorinating agent for inorganic compounds; as a 

catalyst in esterification and halogenation of aliphatic acids: and in the 

nitration of thiophenes and other compounds. Acetylacetone has been 

prepared in 80% yield from acetyl chloride by a three-stage process 

involving an addition compound of acetyl chloride and aluminum chloride. Specialty applications include its use as a catalyst in the esterification of cellulose by acetic anhydride; to accelerate the reaction and 

improve the wetfastness of the resultant yams; in the manufacture of a 

pour-point depressant for lubricating grease; as a stabilizer against 

polymerization of organic isocyanates or diisocyanates; and as a rubber' 

antiscorch agent. 

Physic*! and Chemical Properties 

Acetyl chloride has mp -112.86°C, bp 51.8°C, flash pt 4.5°C. d'f 

1.1051 g/cm3, nj,0 1.38708, surface tension 26.7 - 1.0 mN/m ( = dyn/cmi 

at 14.8°C and 21.9 mN/m at 46.2°C, latent heat of fusion A( W, ) (Uquid) 

275.3 kJ/mol (65.8 kcal/mol), and bond dissociation energy of 

carbon-chlorine bond 320.9 kJ (76.7 kcal). 

It is soluble in acetone, glacial acetic acid, ethyl ether, benzene, 

toluene, chloroform, and carbon disulfide, and is used as a solvent. 

Acetyl chloride decomposes vigorously in water to form acetic acid and 

hydrochloric acid. It reacts with alcohols and amines. Acetamide is 

formed by treating acetyl chloride with anhydrous ammonia or with 

concentrated aqueous ammoniacal solutions. Potassium sulfide and 

potassium hydrogen sulfide react with acetyl chloride to form acetyl 

sulfide and thioacetic acid. Acetyl chloride reacts with acetylene at locC 

in the presence of aluminum chloride to give methyl vinyl ketone. Acetic 

anhydride is formed in the reaction of acetyl chloride with sodium 

acetate. It decomposes at 400°C over a nickel catalyst into carbon 

monoxide (62%), hydrogen (32%), hydrogen chloride, ethylene, and carbon 

dioxide. It reacts with zinc, aluminum, and other metals to form the 

chloride of the metal and a variety of organic compounds. 

Preparation 

Large scale in situ industrial production of acetyl chloride uses the 

action of hydrogen chloride at 85-90cC on acetic anhydride, to produce 

a practically quantitative yield. Commercially, it is prepared by treating 

sulfur dioxide and chlorine with sodium acetate followed by distillation. 

Laboratory manufacture involves the reaction of phosphorus trichloride 

with acetic acid. Industrial equipment for acetyl chloride is usually made 

of glass, glass-lined steel, Teflon, Teflon-lined steel, or heavy-wall polyethylene. 

Acetyl chloride is shipped in 220-L (58-gal) polyethylene-lined drums 

and in 100-g and 500-g packages. It carries the U.S. DOT White Label 

designation for a corrosive substance. It is produced in both a practical 

and a reagent grade. 

Health and Safety Factors 

Acetyl chloride violently decomposes with water and alcohol and is 

easily hydrolyzed into acetic acid and hydrochloric acid by body moisture. It has a toxic effect of its own because it reacts with the SH group 

of protein molecules. It is highly toxic and corrosive and a strong 

irritant. It must be used with adequate ventilation, and proper protective clothing should be worn. Its vapor forms explosive mixtures with air. 

Spills or leakage of acetyl chloride should be treated with sodium 

bicarbonate. 

THERESA A. MORETTI 

American Hoechst Corporation 

G.A. Olah, Friedel-Cra/ts and Related Reactions, Interscience Publishers, a 

division of John Wiley & Sons, Inc.. New York, 1963. 
AL-W) 

Shrcvc'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.87 

768 Chap. 34 Palroehmmleala 

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

yield possible. (4) Lower molecular weight paraffin hydrocarbons are onidized non ******* 

cally to produce mixed compounds, among them acetaldehvde and acetic acid S»

 C yn* 

such mixtures is difficult.

 3eP*'«ion of 

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

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

already cut deeply into the market. **** 

.Acetic acid is widely used, and much is converted to acetic anhvdride.11 

Eastman12 is currently building a very large plant to produce these and other che 

from coal. The reaction between ketene and acetic acid produces the anhvdride bu^'h* 

amount of energy required to produce the ketene iacetone is cracked to give ketene' ' 

methane) is very large.

 incl 

3|l 

lv 

,CH,),CO - CH2=-C-0 + CH, 

CHj-C= 0 + CH3COOH - (CH,COiiO 

Ketene is used immediately after manufacture because it does not store well. The mawr < 

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

Ethylene glycol,** used in antifreeze, 40 percent, and in fibers and films. 50 percent is 

major petrochemical and has been for many years. The demand in 1981 was 2 X IQ9 ' 

Like most of the other alcohols, it was originally made by reacting chlorine and water HOCl'. 

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

procedure and several others (formaldehyde + COt, fermentation, oxidation of propane 1 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 catalvst to l<>rm 

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

oxide, then convert it to glycol by hydration. During the hydration, however, polygly, 0ts 

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

H,C=CH , • 1/2 Oj 

MiO 

CH,—CH, * (CO, »nd H2 0 by combustion 1 

\ / 

0 

CH,—CH, * H,0 CH,—CH2 * polyiiycoU 

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 COt, 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. CHEhATECH 1(10) 600 (1971). 

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

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

^Hydrocarbon Process. 80 (11) 161-163 (1981). 
r 

P.88 

SH-3?7 

fourth edition 

CHEMICAL 

PROCESS 

INDUSTRIES 

R. NORRIS SHREVE 

Late Profeuor Emeritus of Chemical Engineering 

Purdue University 

JOSEPH A. BRINK, JR. 

Consulting Chemical Engineer 

Profet$or and Chairman of Chemical Engineering 

Washington State Univenitv 

McGRAW.HILL BOOK COMPANY 

New York St. Louis San Francuco Auckland Bogotd 

DOutldorf Johannetburg London Madrid Mexico 

Montreal .Vmr Delhi Panama Paris SOo Paulo 

Singapore Sydney Tokyo Toronto 

RADIAN LIBRARY 

DURHAM, N.C. 
Library of Congress Cataloging ia Publication Data 

Shreve, Randolph Norris, 1885-1975. 

Chemical process industries. 

Includes bibliographies and index. 

1. Chemistry, Technical. I. Brink, Joseph A., 

date, joint author. II. Tide. 

TP145.S5 1977 660.2 77-4236 

ISBN 0-07-057145-7 

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

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

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

publication may be reproduced, stored in a retrieval system, 

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

mechanical, photocopying, recording, or otherwise, without 

the prior written permission of the publisher. 

34567890 FGRFGR 7865432109 

The editors for this book mere Jertmy Robinson and Esther Gelatt, 

and the production supervisor was Teresa F. Leaden. 

It was set in Bodoni Book. 

Printed and bound by Fairfield Graphics. 
is consumed in the chemical indust 

r. largely because of enhanced yields 

pment size, and reduced heat ioss ^ 

md vapor phases, using a variety °e 

aeratures (about -I00°C) are em n i„ °, 

teat removal is a large one. Oxiriatir 

ie CO to methanol, hence the \w" 

ipa. Tex., oxidize propane and bUian,. 

ing chemicals. Air has been used h 

ted from employing oxygen. Some ,,(-

••rmaltlehvde. acetaldehvde. ar^i, 

•it oxidation is employed to raise ____[ 

il gas to make acetylene (Chap. 71 

It is reported that Celanese's new 

of titanium vet reported. 

is obtained with oxvgen for anv o\\,* 

•"- . c - ti 

ehyde. formaldehyde, methanol, and 

iffin chain length and the higher the 

-elective: a cobalt catalyst with liquid, 

lereas a manganese catalyst furnisher 

.elanese at Pampa.47 Tex., for butane 

nillion lb in 19761 bv four methodssulfates in sulfuric acid under a presit of reaction). 

Idehvde bv passing through a copperHalogenation and Hydrohalogenation 709 

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

The acetaldehyde is distilled. The conversion and vield 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 many other compounds, acetaldehvde and acetic acid. The selectivity of the process 

is reasonable, only 15 to 20% of the paraffin being oxidized to CO and C02 . and the remainder 

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

Acetic acid51 and anhydride using oxvgen are produced bv the oxidation of acetaldehvde. 

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

The acetaldehyde is oxidized by air with methvl 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 anhvdride and acetic acid. 

are separated and purified in a series of bubble-cap columns, the crude still and the anhvdride 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 emploved in various other acetylations. A development02 has been the production 

of acetaldehyde-monoperacetate (AMP) 

2CH3CHO + 02 

O —HO H 

ultraviolet lighl r u r^ ^ .' 

0°C \ 0-

/ \ 

-0 CH3 

bv the controlled low-temperature oxidation of acetaldehvde. The AMP can be used to produce 

epoxides or 2 mol of acetic acid. 

Ethylene oxide53 is an important chemical intermediate, vielding ethylene glvcol (half of the 

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

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

ethylene: 

C,H4 + iO, 123-300 psi. 

.-atalvst 

CH., 

| \" 

I 

CH, 

0\g) Atf = -3 5 kcal 

= -4 3 kcal 

rectifying to give 99% acetaldehvde. 

loechst49 for the direct oxidation of 

aqueous solution of copper chloride 

th air or oxygen is passed: 

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

Production in 1974 was 4.26 billion lb. 

Aromatic oxidation5* 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 HYDROFORMYLAT10N55 The oxo process is a method of converting a-olefins to 

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

I \'6 K'ill il.-^. njitiun-. rf-lVri-ni'*"-. Ilm,,-harl-. 

!10. 

'.x Profit, pp. J32-234 lriow.:hart for ovidalion 

"Hoechst Reveals Wacker Process, Chem. Eng. iVetra. Apr. 17. 1961. p. 52: Petrochemical Handbook: Pel. Refiner. 

42(11), 1963; Cuccioni. Acetaldehyde via Ethylene Oxidation. Chem. Eng. (V.K). 70(25). 150 (1963). 

"Goldstein, op. eit.. p. 373: Sittig, Acetic Acid and Anhydride. Noves. 1965: Austin. Industrially Significant Organic 

Chemicals. Chem. Eng. (S.Y.). 81(2). 128 (1974). 

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

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

54Phthalic anhydride flowchart. Fig. 34.12; Hydrocarbon Process.. 52(11), 159 (1973). 

55Groggins. op. eit.. pp. 651-693 and particularly p. 683 (kinetics and flow diagram); Goldstein, op. eit.. pp. 204ff.: How 

Oxo Stays in the Race. Chem. Week. June 6. 1964: Hahn, op. eit.. pp. 104-116.