ENGINEERING AND PROCESS DEVELOPMENT
Svnthesis of Dodecvlbenzene I
Y
S Y N T H E T I C DETERGENT I N T E R M E D I A T E M. 1. SHARRAH
AND
GEO. C. FEIGHNER
Confinental O i l Co., Ponca Cify, Okla.
D
URISG the years immediately follom ing Korld \Var 11, the
synthetic detergent industry has attained its greatest period of growth. Table I roughly indicates the accelerated commercial evolution of synthetic detergents in recent years (3-6).
Table I.
Alkylation of Benzene and Fractionation Product Are Basic Steps in Synthesis
In order to provide a basis for dexription oi effects of varialJlrn, a laboratory alkylation using aluminum chlo~itlcip outliricvl : ~ i i i i the experimental results are presontt:J.
Synthetic Detergent Production
Tear
Industrv Production, AIil1;on Pounds
1948 1949 1950 1951 1952
1200 1400 1700
400 700
Abundant source materials and knodedge of continuous flow, large volume operations have enabled the petroleum induqtry to produce a n alkyl aryl hydrocarbon detergent intermediate of high purity under carefully controlled conditions to meet rigid specifications, while consistently decreasing the cost to the consumer. T h e specific alkyl aryl hydrocarbon from petroleum sources, which has become the work horse of the synthetic detergent industry, is dodecylbenzene. Dodecylbenzene, as marketed, is a blend of isomeric, predominantly monoalkyl benzenes, the saturated aliphatic side chains of which average 12 carbon atoms in length. Dodecene and benzene represent the raw materials for dodecylbenxene manufacture, Dodecene is normally obtained by polymerization of propene to the tetramer, and petroleum benzene is made by a reforming operation, such as Hydroforming or Platforming$ on light naphtha. Benzene is alkylated with the propene tetramer in the presence of a Friedel-Crafts catalyst. This paper priinaril? reports the results of dodecylbenxene preparation using thiee different Friedel-Crafts catalysts, aluminum chloride. hT tlrogen fluoride, and sulfuric acid.
Iknzene (445 grams, 5.7 moles), 0.1 gram of water (0.006 molcl, and 8 grams of commercial grade anhydrous aluminum rliloride (0.06 mole) were charged into a reaction flask and vigorously agitated. Dropwise addition of 26:! grams (1.5 moles) of propene tetramer was started with the reactants a t approximately 26" C. The react,ion temperature rose mpidly, and t,he dodecerie addition rate v a s adjusted to maintain a maximum reaction temperature of 56" t o 60" C. Dodecene addition was completed in 30 minutes with tn-o 2-gram portions of catalyst being added 10 and 20 minutes after starting dodecene addition. Stirring was continued for 15 minutes after completion of dodecerie addition. The acidic reaction mixture was neut,ralized by wadiing \vith 100 ml. of aqueous 5% sodium hydroxide. Fractionation of t,he neutralized, crude reaction mixture into four fractions -namely, benzene, an intermediate product.. dodecylbenzene, anti a bottoms material-was accomplished in a true boiling poiut, column with nine theoretical plates. Alkylation and fractionation data are shox-n in Table 11. Typionl IJhysical propertie5 of the products arc shonn in T:ihlo 111. The intermediate fraction contains approximately 62 % alkyl ~ I c l i Z ~ l lhaving ~s side chains vith four lo nine carbon atom.;. Such IOK molecular Twiglit alkyl benzenes are undoubtedly formed hy fragmentation of certain isomeric dodecene structures, follou-ed by alkylation of benzene by thcsc fragments. T h e remainder of t,he intermediate is saturated 1ir.drocarImns cont,aiiiirig approsirnntely 12 carbon atoms, which inn>-1x1 formed by disproportion:%ric~ tion and prrferential cyclimtion of cort:iin i . ~ o n ~ i ~tlotlecene structures.
b
u)
+
5
40
Y
I 8!
20
248
I ,
b
20
I
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
0
Vol. 46, No. 2
ENGINEERING AND PROCESS DEVELOPMENT
Table II.
haborotory Preparation of Dodecylbenzene with Aluminum Chloride ALKYLATIOK
Benzene Grams
445.0 5.7
Aloles
Dodecene Grams BIoles Benzene/dodecene, mole ratio -4luminum chloride, grams Distilled water, gram Seutralized reaction crude, grams Handling lose. grams FRACTIONATIOY Fraction Benzene Intermediate Dodecylbeneene Still bottoma Total Distillation losb
Vapor Temp., C . 80-143 60-121 121-216
Pressure, Mm. Atmospheric 20 20
... ...
...
...
R4w MATEA:ALGossmieTroN
AKD
252.0 1.5 3.8 12.0 0.1 666.3 7.8 Weight of Fraction, Grams 335.2 43.6 211.3 71.4 661.5 4.8
-
COFRODUCT FORVATION Grams/Gram Dodecylbenzene
Benzene conaun~ed l ~ o d e c c n econsumen Aluiiiinum cldoride lnternirdiate formed l3ottom.o former.
0 338
Figure 2.
Table 111.
Typical Physical Properties of Products Intermediate
ASTM D-15Sa Engler Distn. Initial b.p. 5% 10% 50% 90% Final b.p. Specific gravity, 6 O / S O 0 F. Apparent molecular wt. Bromine number Aniline point O F. Refractive inhex (74' F.) Flash poiEt (Cleveland open cup,. F. Viscos;ty, Saybolt Universal see.
Dodecylbenzene Temp., F.--
Bottoms 647 682
....
0,8304 162 0.40 76
1, 4 5 9 5
inno - . _-2000 I?. ff
.. ..
Saybolt color 0 With 1-inch immersion thermometer.
0.8794 232 0.12 45.5 1.4863
715 760 779 0.8702 365 0.50 156 1.4900
260
381
46
..
29
.. ..
57
Dodecylbenzene contains more than 99% alkyl benzenes, which are predominantly monosubstituted, although traces of disubstitution are indicated by infrared analysis. Figures I, 2, and 3 are infrared spectra of samples of dodecylbenzene produced by aluminum chloride, hydrogen fluoride, and sulfuric acid catalysis, respectively. Disubstitution is clearly evident in the spectra of dodecylhenzene prepared from hydrogen fluoride and sulfuric
Infrared Spectra of Dodecylbenzene from Hydrogen Fluoride Catalyst Cell length 0.1 02 and 0.023 mm.
WAVE NUMBERS IN CMI
WAVE NUMBERS IN CM'
WAVE LENOTt4 IN MICRONS
Figure 3.
I
W A K UN6TH IN MICRONS
Infrared Spectrum of Dodecylbenzene from Sulfuric Acid Catalyst Cell length 0.09 mm.
February 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
249
ENGINEERING AND PROCESS DEVELOPMENT acid catalyzed reactions; the absorption band a t 12.05 microns is due to para dialkyl benzenes. The bottoms product contains approsimately 99% alkylbenzenes. A trace of nonaromatic hydrocarbon, which can be isolated by silica gel chromatography, is believed to be produced by polymerization of dodecene, followed by hydrogen transfer in the presence of Friedel-Crafts catalysts. 1%
Benzene Dodecene Ratio and Reaction Temperature Determine Product Distribution and Yield
do
'
;
'
MOLE
Figure 4.
'
E
'
;
;*
; o '
~
k
'
6 RATIO
L
' b ' 0 ' B E N Z E N E / DODECENE
'
14
'
Effect of Benzene to Dodecene Ratio on Dodecylbenzene Yield Sulfuric acid catalyst
mole ratios below 3 to 1 mas not anticipated. This decrease is possibly due to inactivation of the catalyst by formation of stable aluminum chloride complexes. The composition of the intermediate fraction varies as shown in Table V with variarion in the inole ratio.
Effect of Dodecene Concentration on intermediate Composition Konaromatics in Intermediate,
Renzene/Dodecene, hlole Ratio 3.8 7.5 10.0 15.0
1 4 '
'
'
MOLE
Table V.
\ 2
i
'
Figure 5.
Mole Ratio of Benzene to Dodecene. T'ariation in the mole ratio of benzene to doJecene greatly affects product distribution. The relative quantities of dodecylbenzene and bottoms produced, and to a more minor extent, the relative quantities of dodecylbenzene and intermediate produced, are altered. Such variation inmole ratio has no apparent effect upon the cheniical or physical properties of dodecylbenzene.
t sol K
'
%
38.0 34.5 26.0 17.0
RATIO BENZENE /DODEGENE
Effect of Benzene to Dodecene Ratio on Co-product Yields Sulfuric acid catalyst
Table IV gives the results of alkylations using aluminum chloride a t various mole ratios. These results are graphically presented in Figures 4 and 5. Reactions competing l+ith inonoalkylation are fragmentation, hydrogen transfer t o produce alkanes and diolefins, polymerization, cyclization of dodecene, and polyalkylation. All of these competing reactions are favored by increased dodecene concentration in the reaction mixture. Therefore, the results a t mole ratios above 3 to 1, a6 shoFn in Figures 4 and 5, are t o be expected, However, the rapid decrease in bottoms formation a t
Table lk.
Reaction Temperature. Alkylation reactions were performed in which external cooling was applied in order to maintain the reaction temperature within h2.5' C. of the desired temperature. A plot of dodecylbenzene yield in terms of volume per cent dodecylbenzene in the neutralized crude versus reaction temperature, with a constant mole ratio of 3.8 to 1, is shown in Figure 6. Lowering the reaction temperature from 59" to 32' C. will effect an approximate 5 to 7.5% increase in dodecylbenzene yield. Over the entire temperature range, a decrease in dodecylbenzene yield is accompanied by an increase in intermediate yield. This has led to the opinion that above 32' C. the rate of the dodecene fragmentation reaction increases rapidly, while below 32' C. the rate of the alkylation reaction is Loo slow to produce satisfactory yields of dodecylbenzene.
Alkylations with Aluminum Chloride Reaction D a t a
Benzene Grams Moles Dodecene Grams Moles Benzene dode-,ene, mole ratio Aluminum chloride, grams Temp C. DistiliAd water, ram Neutralized crufe, gram Handling loss, grams Benzene Intermediate Dodec ylbensene Bottoms Tqtal Distillation loss, grams Benzene consumed Dodecene consumed Aluminum chloride Intermediate formed Bottoms formed
250
117.0 1.5
175.0 2.24
234.0 3.0
252.0 1.5 0.5 12.0 55-60 0.1 272.8
252.0 1.5 1.0 12.0 55-60 0.1 331.7 5.5
252.0 1.5 1.5 12.0 55-60 0.1 391.7 3.8
252.0 1.5 2.0 12.0 65-60 0.1 453.0 4.0
29.0
73.6 66.2 125.7 60.1 325.6 6.1
58.5 0.75
65.8 125.2 51.4 271.4 1.4 0,235 2,013 0.096 0,525 0,410
445.0 5.7
585.0 7.5
252.0 1.5 3.8 12.0 55-60 0.1 661.0 11.0
252.0 1.5 5.0 12.0 55-60 0.1 808.0 4.0
True Boiling Point Distillation Results, Grams 251.5 335.2 326.7 89.2 148.2 41.1 43.6 45.7 47.5 52.9 194.6 211.3 219.4 176.3 184.2 75.2 7 1 . 4 67.0 67.0 70.0 562.4 661 5 385.4 449.9 3.1 14.1 4.8 2.2 6.3
468 2 43.2 238.0 57.0
0.345 2,005 0,095
0.526 0.478
362.7 4.65
445.0 5.7
m 806.4 1.6
~
Grams/Gram Dodecylbenzene 0.468 0.571 0.520 0.487 1.368 1.295 1.193 1.429 0.062 0.057 0.068 0.065 0.258 0.211 0.206 0,300 0.338 0.380 0.386 0.380
0.540 1.149 0.055 0.208 0.305
0,491 1.059 0,050 0.181 0,239
INDUSTRIAL AND ENGINEERING CHEMISTRY
878.0 11.25
1,170 15.0
1,755 22.5
252.0 1.5 7.5 12.0 55-60 0.1 lOQ9 13.0
252.0
252.0
748.0 41.1 257.8 49.0 1095.9 3.1
1039 29.5 274.1 48.0 __ 1390.6 3.4
1600 33.4 2i7.9 46.0 1957.3 8.7
0,504 0.978 0.047 0.159 0,190
-
0.478 0.920 0.044 0.108 0.175
0.558 0.907 0.043 0.120 0.166
Vol. 46, No. 2
ENGINEERING AND PROCESS DEVELOPMENT Quantity of Catalyst. Little can be said regarding quantity of catalyst except that a certain minimum amount of aluminum chloride is required in order to obtain substantially complete reactions. If the alkylation reaction stops during dodecene addition because of insufficient catalyst, reinitiation by addition of more aluminum chloride is extremely difficult. However, utilization of more than the minimum amount of catalyst is undesirable.
gen fluoride in the reaction flask. The remainder of the benzene was mixed with 252 grams (1.5 moles) of dry dodecene in the dropping funnel. The benzene-dodecene mixture was added dropwise in approximately 30 minutes, while the reaction mixture was stirred vigorously and the reaction temperature was maintained at - 1' to + l o C. The reaction mixture was stirred for 60 minutes after the addition of benzene-dodecene was completed and then poured over ice in a beaker. The dilute hydrofluoric acid layer was discarded, and the organic layer was washed twice I
2
NVI
g a 20m
3.8 UOCES BENZENE I MOLE OODEGENE 00416 9 l l G l l / OOOECENE
+
B REAOTION TEMPERATURE, .G
Figure 6.
DODEOILBENLENE, QRbW -10
Effect of Reaction Temperature on Dodecylbenzene Yield Sulfuric acid catalyst
MOLE RATIO BEMZENE I OODECENE
Figure 7. EfFect of Benzene to Dodecene Ratio on The alkylation reaction will not proceed under anhydrous conProducts ditions if aluminum chloride alone is used as the catalyst. Either Hydrogen fluoride catalyst anhydrous hydrogen chloride must be added as a catalyst promoter or water must be added to the reaction mass in order to create hydrogen chloride by reaction with a portion of the aluminum chloride. Table VI. Effect of Benzene to Dodecene Ratio on Hydrogen Fluoride Recycling of Bottoms. The bottoms Catalyzed Alkylation product from one reaction batch can be Reaction Data recycled to a subsequent batch in order 0 0 0 0 0 0 Temp., C . Benzene to repress formation of bottoms. Alter445 445 585 878 ,070 780 Grams 13.72 10.0 natively, the bottoms may be treated 6.7 5.7 7.5 11.25 Moles with benzene in the presence of anhy252 168 1.5 1.0 drous aluminum chloride in order to 9.15 10.0 120 120 achieve disproportionation and addi,322 948 tional dodecylbenzene yield. However, ,298 900 24 48 utilization of such procedures involves additional catalyst consumption. True Boiling Point Distillation Results, Grams Sulfuric Acid Catalyst Product Contains Unsaturated Contaminants
Three catalyets, anhydrous aluminum chloride plus a hydrogen chloride promoter, anhydrous hydrogen fluoride, and sulfuric acid, were investigated. Alkylations using hydrogen fluoride catalysis a t various benzene to dodecene mole ratios were performed as follows: Approximately 120 grams (6 moles) of anhydrous hydrogen fluoride were weighed into a cold, Monel metal, three-necked, 2-liter flask, which was equipped with a stainless steel stirrer, a stainless steel thermometer well, and a dropping funnel. The reaction flask was immersed in a water-ice-salt bath. Of a definite quantity of dry benzene, 100 ml. were added to the hydroFebruary 1954
Benzene Intermediate Dodecylbenaene Bottoms Total Still loss
331.4 20.3 255.9 70.0 677.6 0.4
330.0 15.3 250.5 63.0
658.8 4.2
465.4 15.2 255.9 61.0 797.5 3.6
762.0 18.5 270.1 52.0 1,102.6
4.4
946.0 14.5 287.1 50.0
1,297.6 0.4
670.0 11.4 180.0 38.0 899.4 0.6
Resulre Reralcclated on Basis of 20 Grams Over-r.ll
nenipne Internedurc Dodecylbenzene
1.033
for Cornparkon. G r a i n s
331.4
339.1
476.8
767.1
010.2
20 3
15.7
15 0
18 6
14.5
255 8
257.4
262.2
271.9
283.1
Rottonis
70.0
61.7
62.5
52.3
50.2
Dodez 'benzece, 5 ul tlieorerirel yield'
69.34
D9.76
71.05
73.68
78.07
(58 8 ) a
Product Tie!d and Raw Material Consulnixion. Gralns,'Grem Dodecylbenzene 0.419 0,415 0.408 0,444 0,411 Benzene 0.927 0.875 0.961 0.985 0.979 Dodecene 0,068 0.050 0.061 0,059 0.079 Intermediate 0.192 0.174 0.251 0.238 0.274 Bottoms Dodec Ibenzene, % of theoretical yield' 69.3 69.8 71.1 73.7 78.1 Q
691.3
(lIO3iP 11.a (17.7)a 185.7 (278.6)" 30.2 75.6 (75 5)"
;:io4 0.084
0.211
76.6
10 t o 1 mole ratio benzene t o dodeoene results recalculated to a basis of 252 grams dodecene charged
for comparison.
INDUSTRIAL AND ENGINEERING CHEMISTRY
251
ENGINEERING AND PROCESS DEVELOPMENT
__
furic acid, depending Table VII.
OII
tl;c
Effect of Reaction Temperature on Hydrogen Fluoride Catalyzed Alkylation
Iiewtion Data
Reaoaion temp., Benzene
C.
0
Grams Moles
44;
Dodecene
0
0.7
232
Grams
9loles ilydrogen 3uoride grama Totiti hydrocarbin charged, grains
l..j
120
697
J
7
- 10
441
6i8
876 11.25
878
878 11.25
23'2 1 5 120
252 1.5 120
252
232 ; 3
J
232 1 5 120
252
097 863 34
1387 083
7
0
I1 2 3
1.5
I20
1,130
1,130
1,100
1,107
Xeutralized crude, prams Tot&!hydiocarbon 1038 gia!i,s
678
Bewetie Intermediate Dodecglbenzene
Triie Urnling 1'0.n: Disrillation Readits, Grains 931.4 330.0 327.3 $49 782 20.3 I3 3 13.2 2i 9 18.5 235.9 2.50.3 274.2 242.2 2TO.1 7 0 0 0 3 . 0 6 , j . Z 62.0 a 2.n ...---____-_I1,102.6 67Q g 1,095.1 038.8 677 0
Bottoiiis Total
19
0.4
Still loas
2::
30
1.1
3.1
4 2
+
+10
4.9
10
11.23
1.: 120
1,130 1,105 25
73,
120
?,I80 1 ,110 20
7.53 22.3
12.I 287.1
285.6
50.0 1,093.2
I , 110.9
4 4
9.8
767.1
766.2 12.3
so.0
the catalyst layer $vas mt,zd. The hydrocarbo
-0.9
liekuirs Recalcdated on Raois of 20 Grams Over-211 Loss for Coinparison. Grams
Benzene
Interniediate Dodeeylhenzene
Dottol1:s Ilodecylhenaene cal yieid
of t1ieore:i-
331 313 255 7(!
4
3 0 0
69 3-j
?
339. I 13.7 3.j7.4 64.7
32,; 13 I 273 0 61 R
i75.5 22.2 2.13.5 62.8
7 3 !I8
Wiii
66.53
18.6 271.9
52.3 i3.68
291.0 50.7
78.86
Pradrict 1-ield a n d Raw hIat,eiicl Coniumgtion, Ciiams/Gram Dodecylbenaene 0 460 0.400 0.423 11 459 0,429 (I 444 I 026 0.92i 0.877 1.00! 0.019 0.985 0.06~ o 091 0.042 0 om o ofiL o . n ~ s intermediate iorincd 0 256 0.192 0.174 @ ~ ' i i 0.238 0.zi.i Bottoms f o n n e d
Benzene coiiauiiied Dodecene consumed Dodecylhenaene. retire: sieid
oi t l m -
69.34
'JR 76
73.08
66.Z3
325
I
225
LA---&--
LO
-10
REbCTIOY T E M P E M T U R E ,
*C
Figure 8. Effect of Reaction Temperature on Dodecylbenzene Yield Hydrogen fluoride cafalysl
with 200-1111. portions of xater before neutralization with 5% aqueous caustic. Fract,ionation of the neutralized crude was accomplished in a true boiling point, colunin xit,h nine t,heoretical plates. Alkylation data and yields are shown in Tahle TI,and the result,sare plotted in Figure 7. Allcylatioiis using hjdrogen fluoride catalj-sis vere also performed at various temperatures at both 7.5 to 1 miti 3.8 t,o 1 benzene to dodecene mole ratios. A reaction was performed at hydrogen fluoride reflux temperature (19.4' C,), using a copper reflux condenser cooled with ice rvater. Results of the tempeiature study are shown in Table VI1 and Figure 8. Alkylations using sulfuric acid catalysis nero performed according to the following procedure:
9 definite quantity of benzene, depending upon the mole ratio involved, was charged into a threenecked reaction flask which vas immersed in an ice-\mter bath. A definite quantity of sul252
i X 22 a 285.6
innspheric pre4sut.e lo
50 0
77 413
9 4.3
280' C. Decomposition of by-product dialkyl su1f:itc.s oc-
0.88
0.07 0.1;
yield acidic, d e c o r n p o h i i iciii
products and .w'r"re darlteni,i~. In order to remove tllc i!k composi t i o n urotluc is. t1.t benzene-free 'crucii: n ; i < washed with 2% i q w i g i L i of 96.595 sulfuric :wit1 aiLii again neutrnlizcil n-ill1 aqueous caustic before fractioii:itinp :; d u c e d pressure in a truc boiling point column rrith !?irie iheorctical plates.
73.65
73.86
ii.4
using hydrogen fluoride or aluminum chloride catal) containing 9G.5 to 100% sulfuric a d operates satisfactor furic acid is inoperable. At high acid strengths, t,hc crJnvci.ici:! of dodecene to bottoms is increased. Quantity of sulfuric acid catalyst, is critical in that a niiniiii!.m quantit,yis required, relative to the total quantity of hydrociirh,,ii involved, rather than relative to the amount of dodecene. ;\s the quantity of the catalyst is increased, the conversion of ilodecene to bottoms is increased. As the mole ratio of benzct ciodecene is increased, the yield of dodecylherizcne also incre hut, this effect is closely interrelated wit,h cahlyst quantity. Allthough the procedure outlined for sulfuric acid cittalysi. yields a mater-white product, the bromine number of the produrt is high. The un3aturatee contributing 'Lo the high bromine nui:iber lie prerlominanily in the higher boiling portion of the dodcc! Ibenzene fraction. Removal of approximately 15% of the lli boiling portion of tlic product, vr-ill reduce the bromine nnmbcr .if t,he remainder to approximately unity. Variation in Raw Materials. Laboratory alkylations indicate that either coal tar or petroleum benzene is satkfact,ory. Dodecene for the production of detergent intermediates iilil:: be carefully selected. Triisobutglene is susceptible to fregnic11t~~;tion, and high yields of di-terl-butylbenzene are obtained iE alkylat,ion of benzene c d h this polymer (1 is attcmpt.eii. Im& ( Z j has pointed out that dodecene obtainod by polyincirizxtion of propylene contains olefins of the follox-ing structnrrs, among others:
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Vol. 46, No. Z
ENGINEERING AND PROCESS DEVELOPMENT
Effect of Acid Concentration on Sulfuric Acid Catalyzed Alkylation
Table VIII.
(Reaction temperature 5' t o 10' C.) Reaction D a t a
7.5 80 138.7 252 878 1,130
Benzene/dodecene inole ratio Sulfuric acid concd., 70 Sulfuric acid. ml. Dodecene, grams Benzene, grams Total hydrocarbon charged, giains Reaction loss, grams Catalyst layer, grams Hydrocarbon loss to catalyst layer. grams
7.5 90 113.3 252 878 ,130
... ... ...
0
7.5 96.5
7.5 94 100 252 878 1,130
252 878 1,130 28 193 9
. I .
191 7
252 878 1,130 44
... ...
7.5 97.6 100 252 8'18 1,130 43 198 14
7.5 101.2 100 252 878 1,130 36
1,086 758.0 30.7 256.7 23.0 1,068.4 17.6
1,087 755.0 20.0 270.4 32.0 1,077.4 9.6
1,094 773 0 21.4 253.5 39.0 1,086.9 7.1
7.5
96.5
100
100
7.5
102.5 100 252 878 1,130
... ...
...
.. ...
True Boiling Point Distillation Results, Grams
1,130 878.0 214.0
Charge Benzene Intermediate Dodecylbenzene Bottoms Total Still loss
30.0
2.0 1 ,123.0 7
1,102 782.0 29.0 259.0 30.0 1,100.0 2
78810
8k5:O 184.0 59.0 5.0
38.2 233.8 21 . o
...
... ...
...
7jQ:O 22.8 246 4 44 0
...
...
Yield, Grams/Gram Dodecylbenzene
.8.400 .. 7.133
Dodecene Benzene Intermediate Bottoms Dodeoylbenzene, % of theoretical yield
4.271 0.390 3.119 0.085 15.9
0.667 8.1
Table IX.
1,078 0.385 0.163 0.090 08.4
0.973 0.371 0.112 0.116 70.2
0.982 0.467 0.120 0.090 69.6
0.932 0.485 0.074 0.118 73.2
0.994 0,414 0.084 0,154 68.7
1.022 0.564 0.093 0.179 G6,8
Effect of Quantity of Acid on Sulfuric Acid Catalyzed Alkylation (Reaction temperature 5' to 10' C.) Reaction D a t a
7.5 96.5
Renaene/dodecene. mole ratio Sulfuric acid concn., Sulfuric acid, ml. Dodecene, grams Benzene, grams Total hydrocarbon charged, grams Reaction loss, grams Catalyst layer grams Hydrocarbon I'oss t o catalyst layer, grams
50
252 878 1,130 24 98 6
7.5 96.5 100
252 878 1,130 28
... ...
7.5 96.5 200 252 878 1,130 30 390 22
7.5 96.5 300 252 878
... ...
686 34
7.5 96.5 367 252 878 1,130 27 704 29
3.8 96.5 100
252 445 897 22 192 8
5
96.5 100
202 585 837
.. .. .. ...
5 96.5 148 252 585 837
...
284 12
3
D6.S 1,000
232 58.5
837 16
... ...
True Boiling Point Distillation Results, Grams
1,106 827
Charge Benzene Intermediate Dodecylbenzene Bottoms Total Still loss
60
189 2 4 1,100 6
1,102 782 29 259 30 1,100 2
1,100 746.0 24.5 298.1 22 5 ___ 1,091.1 819
75i:o 17.7 291.7 26.0 __ 1,086.4
...
1,103 764 o 20 7 267 2 33 0 ___ 1,084 9 18.1
675 357 24.5 274,s 18.0 __ 674.3 0.7
...
485 30.1 277.4 24.0
489 ' 21.8 274.9 29
..*
...
...
...
822 485 19 273,i 41.0 __ 818.7 3.3
Yield, Grams/Gram Dodecylbenzene
1.333 0.270 0.317 0,127 51.2
Dodecene Benzene Intermediate Bottoms Dodecylbenzene, % of theoretical yield
0.973 0,371 0.112 0.116
70.2
0.845 0.443 0.082 0.075 80.8
0.864 0.435 0.061 0.089 79.1
0.943 0.917 0.908 0.917 0.427 0.320 0.360 0,349 0.078 0.089 0.109 0.079 0.124 0.066 0.087 0,105 72.4 74.5 75.2 74.5
0 921
0,360 0,069
0.150 74.2
Summary
R'
\ C=CHZ /
Lewis has further shown that olefins of the former structure are preferred, since olefins of the latter structure, which are typical of polyisobutylene polymers, tend to fragment rather than alkyR late.
Olefins of the
\
C 4 H 2 structure polymerize much
/ R' H H
I
1
more readily than olefins of the R-C=C-R' structure, and may therefore be removed from the dodecene by treatment with a polymerization catalyst prior to alkylation.
February 1954
Bluminum chloride, hydrogen fluoride, and sulfuric acid n eie investigated as catalysts in the preparation of dodecylbenzene from benzene and propene tetramer. The effect of the mole ratio of benzene to dodecene on the distribution of products and the effect of reaction temperature on the yield of dodecylbenzene were studied with aluminum chloride catalysis. The rate of increase in yield of dodecylbenzene uith increasing mole ratio is rapid until a mole ratio of approximately 6 to 1 is reached. With higher mole ratios, the rate of increase is slower. Conversely, the yield of intermediate material boiling below dodecylbenzene decreases rather rapidly between moIe ratios of 1 to 1 and 6 to 1, and with higher mole ratios, becomes essentially constant. The amount of material boiling above dodecylbenxene is a t a maximum a t a mole ratio of 3 to l, decreases rapidly at lower mole ratios, and decreases gradually a t higher mole ratios. Bottoms formation can be controlled by recycling bottoms or by increasing the ratio of benzene to dodecene. At a mole ratio of 3.8 to 1, it was found that the reaction temperature which gives the best yield of dodecylbenzene is 32" C.
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
253
ENGINEERING AND PROCESS DEVELOPMENT At comparable mole ratios of benzene to dodecene, sulfuric acid gives higher yields of dodecylbenzene than hydrogen fluoride or aluminum chloride. However, the products from sulfuric acid catalysis are contaminated with undesirable olefins which are difficult to remove. Coal tar benzene can be used interchangeably with petroleunl benzene, but polybutenes cannot be substituted for polypropenes. Acknowledgment
and B. & Young, I. in obtaining some of the data and in editing this paper, is greatly appreciated. LiteratureCited (1) Ipatieff, V. N., andPines, H., J . Am. Chem. Soc., 58, 1056 (1926). s. Patent 28477,383 (lg39). (3) Snell, F. D., Chem. Eng. News,29, 36-7 (1951). (4) &d., 30, 30-1 (1952). (5) Ibid., 31, 3 8 4 0 (1953). (6) Snell, F. D., and Kimball, C. R., Soap Sanit. Chemicals, 27, 27-9
**
(1951).
The authors wish to acknomledge the help of R. S. LPunger, niho interpreted the infrared spectrophotometric data. ~h~ assistance of E. L. Hatlelid, J. C. Kirk, E . L. Miller, A. C. Shotts,
RECEIVEDfor review September 2 , 1953. ACCEPTED October 27, 1953. Presented as part of the Symposium on Petrochemicals in the Postwar Years before the Division of Petroleum Chemistry at the 124th Meeting of the CHESIICAL SOCIETY, Chicago, 111. AYERICAN
Ammonium Compounds ALGAE CONTROL IN INDUSTRIAL COOLING SYSTEMS J. I. DARRAGH AND R. D. STAYNER California Research Corp., Richmond, Calif.
s
TTHETIC alkylbenxenes derived from certain petroleum hydrocarbons have achieved a high degree of success commercially as chemical intermediates for the preparation of alkylbenzene sulfonate detergents. As evidence of their progress, the production of synthetic detergent formulations, many of which contain alkyl benzene sulfonates, reached a volume of 1.5 billion pounds in 1951 (6). Dodecylbenzene is a synthetic alkyl benzene prepared from the C1, to CIEfraction of polymerized propene (5). (Dodecylbenzene is used in this paper to describe a commercial alkyl benzene vith an average of 12 carbon atoms in the side chain and is not intended to refer t o a pure compound.) It is particularly suited for application as a detergent intermediate for several reasons, namely:
Cationic Surface Active Agents Derived from Dodecylbenzene Are Synthesized
The preparation and some of the properties of two types of cationic surface active agents derived from dodecylbenxene are described. These compounds were prepared as follows:
~~-D~decylbenzyl-N,N,~~~trimethylammonium chloride
(CH3)sN
C I & - C-/ ~ C H Z ! ~ ( CH,),
6l
hT,N,N-Trimethyldodecylanilinium methosulfate
Preparation of the alkyl benzene and its sulfonate is readily adaptable to large scale operation. Availability of raw materials and the economics of processing are favorable. Sodium dodecylbenxene sulfonate possesses good over-all performance characteristics. Increasing demand for dodecylbenzene has been met by expanded and improved facilities for its production, and it nom occupies an important position in the field of petrochemical intermediates. A consideration of the chemical structure of dodecylbenzene suggests that the material should be capable of undergoing many of the reactions characteristic of benzene and of branched-chain aliphatic hydrocarbons. Therefore, the material is of interest as a chemical intermediate for a variety of chemical products. For example, the lipophilic nature of the alkyl benzene residue suggests its utilization as an intermediate for cationic surface active agents. Several quaternary ammonium compounds in the molecular weight range of 250 t o 400 are used commercially in textile finishing, ore flotation, and as germicides for sanitization and disinfection. Thus, established and potential-use applications for certain related cationic surface active agents provided an incentive for the work dejcribed in this paper.
254
The dodecylbenzene used was Oronite Alkane. All other chemical reagents were obtained from commercial sources and used without further purification. N-Dodecylbenzyl-N,N,N-trimethylammoniumChloride. Dodecylbenzene was chloromethylated by the method of Blanc (1, +$),modified by the use of glacial acetic acid as a solvent ( 2 ) . The crude dodecylbenzyl chloride was vashed thoroughly with r a t e r and then condensed with the stoichiometric quantity of trimethylamine in an aqueous-alcoholic solution. Unreacted dodecylbenxene was removed by extraction with petroleum ether and i2T-dodecylbenxyl-S,-~r,N-trimethylammonium chloride was obtained by evaporation of the solvent as a pale yellow, glassy solid.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 46, No. 2
