INDUSTRIAL AND ENGINEERING CHEMISTRY
1746
(15) Byrne, T. J., and Jenkins, F. M., Oil Gas J., 48, No. 46, 275 (1950). (16) Caesar, C. H., Pdroleum Processing, 4,887 (1949). (17) Conn, A. L., and Brackin, C. W., IND.ENG.CHEK., 41, 1717 (1949). (18) Conn, A. L., Mwhan, W. F., and Shankland, R. V., Chem. Eng. Progress, 46,176 (1950). (19) Curran, M. D., Oil Gaa J.,48, No. 15, 100 (1949). (20) Egloff, G., Zbid.,47, No. 47,162 (1949). (21) Fenex, J. E., Hope, A. W., and Friedman, L., Petrohm Refiner, 28, No. 8, 103 (1949). (22) Feuchter, C. F., C h Eng. Progress, 45,644 (1949). (23) Fisher, F. R., Oil Gas J.,47, No. 47, 160 (1949). (24) Foster, A. L., Petroburn Engineer,21, No. 8, C-7 (1949). (25) Ibid., 21, No. 12, C-6 (1949). (26) Frame, A. P., Oil Gae J., 47, No.47,177 (1949). (27) Gary, J. H., Petroleum ProcesPing, 4, 1104 (1949). (28) Gees, L., Petroleum &finer, 29, No. 3, 110 (1950). (29) Glasgow. A. R., Willingham, C. B., and Rossini, F. D., IND. ENG.CHEM.,41,2292 (1949). (30) Greensfelder, B. S., Voge, H. H., and Good, G. M., Ibid., 41, 2573 (1949). (31) Grenall, Alexander, 41, 1485 (1949). (32) Haensel, V., Oil Gae J . , 48, No. 47, 82 (1950). (33) Haensel, V., and Sterba, M. J., IND.ENG.CHEM.,40, 1660 (1948). (34) Bid., 41, 1914 (1949). (35) Hardcastle, C. A,, Oil Gas J., 48, No. 46, 261 (1950). (36) Hepp, H. J., S w r d , F. P., and Randall, J. H., IND.ENG. CHEM.,41, 2531 (1949). (37) Howard, G. E., Petroleum Refiner,29, No. 3, 107 (1950). (38) Hughes, E. C., Stine, H. M., and Darling, S. M., IND.ENG. CHEM.,41,2185 (1949). (39) Jackson, W. K., Oil Gas J., 47, No. 47,232 (1949). (40) Kastens, M. L., and Sutherland, R. E., IND.ENG.CHEM.,42, 582 (1950). (41) Kearby, K. K., Ibid., 42,295 (1950). (42) Kennedy, R. M., and Hetzel, S. J., Ibid., 42, 547 (1950). (43) Kincannon, L. E., Oil Gas J.,47, No. 47,207 (1949). (44) Luton, R. E., Ibid., 47, No. 47,213 (1949). (45) McKean, R. A., and Grandey, L. F., Chem. Eng. Progress, 46, 245 (1950). (46) McMurray, S. R., Petroleum Processing, 5, 26 (1950). (47) McReynolds, H., and Barron, J. M., Petroleum Refiner, 28, No. 4, 111 (1949). (48) Madorsky, S. L., Science, 111,360 (1950). (49) Madorsky, S. L.,Straus, S., Thompson, D., and Williamson, L., J. Research Natl. Bur. Standards, 42, 499 (1949). (50) May, D. R., Ssunders, K. W., Kropa, E. L., and Dixon, J. K., Faraday Society, “General Discussion on Heterogeneous Catalysis,” April 1950.
GEORGE F. LIsK, ALLIED CHEMICAL
Vol. 42, No. 9
(51) Milliken, T. H., Jr., Mills, G. A., and Oblad, A. G., Ibid., April 1950. (52) Mills, G. A,, Boedecker, E. R., and Oblad, A. G., J . Am. Chem. Soc., 72, 1554 (April 1950). (53) Morgan, D. G., OiZGas J., 47, No. 47,218 (1949). (54) Murphy, M. T., and Duggan, A. C., J. Am. Chem. Soc., 71, 3347 (1949). (55) Neal, H. A,, and Ames, C. B., Petroleum Engineer, 21, No. 8, C16 (1949). (56) Olsen, C. R., and Sterba, M. J., Chem. Eng. Progress, 45, 692 (1 949). \ - - - - ,
(57) Partington, R. G., Stubbs, F. J., and Hinshelwood, C. N., J . Chem. SOC.,1949, 2674. (58) Peavy, C. C., Weinrich, W., Hornaday, G. F., and Noll. H. D.. Petroleum Refiner,28, No. 6, 117 (1949). (59) Ramser, J. H., and Hickey, J. W., Petroleum Processing, 4, 776 (1949). (60) Richardson, R. W., Johnson, F. B., and Robbins, L. V., Jr., IND. ENG.CHEM.,41, 1729 (1949). (61) Robertson, A. J. B., PTOC. Roy.SOC.(London), 199, 394 (1949). (62) Rosenberg, L. M., Doklady dkad. Nauk S. S. S. R, 64,401 (1949). (63) Schall, J. W., Dart, J. C., and Kirkbride, C. G., Chem. Eng, Progress, 45,746 (1949). (64) Schutt, H. C., Ibid., 43, 103 (1947). (65) Schutte, A. H., Oit Gas J.,48, No. 26,70 (1949). (66) Schutte, A. H., and Offutt,W. C., Ibid., 48, No. 10,QO(1949). (67) Schutte, A. H., and Offutt, W. C., Petroleum Processing, 4, 769 (1949). (68) Siecke, P., Oil Gas J.,47, No. 47, 186 (1949). (69) Stubbs, F. J., and Hinshelwood, C. N., Proc. Roy. SOC.(London), 200 A, No. 1063, 458 (1950). (70) Stubbs, F. J., and Hinshelwood, C. N., Ibid., 201 A, Y o . 1064,18 (1950). (71) Sutherland, R. E., and Hanson, D. D., Oil Gas J . , 48, No. 50. 177 (1950). (72) Tamele, M. W., Faraday Society, “General Discussion on Heterogeneous Catalysis,” April 1950. (73) Thomas, C. L., IND. ENG.CHEW,41, 2564 (1949). (74) Thomas, C. L., Hickey, John, and Stecker, Glen, Ibid., 42, 866 (1950). (75) Thomas, E. J., Oil Gas J.,48, KO.46, 221 (1950). (76) Thornton, D. P., Petroleum Processing, 4, 1336 (1949). (77) Ibid., 5 , 45 (1950). (78) Tvy,V. V., Petroleum Refiner, 29, No. 3, 102 (1950). (79) Zlhl, W. C.. Petroleum Processing, 5, 33 (1950). (80) Ibid., p. 361. (81) Weber, G.. Oil Gas J., 48, No. 30, 58 (1949). (82) Ibid., 48, No. 36, 51 (1950). (83) Ibid., 48, No. 49, 60 (1950). (84) Welsh, A. F., Petroleum Processing, 5, No. 2, 157 (1950). (85) Wrightson, F. M., Anal. Chem.,21, 1543 (1949). RECEIVED June 27, 1950.
NATIONAL ANILINE DIVISION,
DYE CORPORATION, NEW YORK, N. Y.
ITERATURE information concerning sulfonation is reviewed for the period beginning with the latter part of 1948 and continuing to about the end of 1949. The scope and coverage indicatad in the first (1.94) and second (1.95) reviews are continued.
THEORETICAL CONSIDERATIONS ALlPHATlC COMPOUNDS
Saturated Direct Sulfonation. COMPOUNDS CONTAINING SULFUR TRIOXIDE. Recent publications continue to emphasize the inertness of paraffinic hydrocarbons t o sulfonation with compounds containing sulfur trioxide (SS). AE in the past, the literature is directed not to sulfonation of p a r a h s per se but rather to sulfonation of mixtures containing p a r a h together with naphthenic or other more reactive hydrocarbons in order to produce
sulfonate products in improved yield and/or quality (77, 158, 155). Thus, Mitchell (138) pretreated and then sulfonated mineral oil extracts with sulfuric acid with the aid of an amphoteric element halide-e.g., stannic chloride, boron trifluoride, and sodium borofluoride-in an inert solvent such as liquid sulfur dioxide, in order to inhibit formation of color and odor in the resulting sulfonate detergents. Ruedrich (155) added, prior to sulfonation, about 12% of an oil-soluble petroleum sulfonate to naphthenic-type lubricating oils in order to decrease acid sludge formation and to increase the yields of resulting oil-soluble sulfonates by 10 to 36%. Gilbert (77) sulfonated substantially aromatic petroleum lubricating oils with acid sludge obtained from the sulfonation of petroleum lubricating oil fractions with sulfuric acid. He found that the yields of resulting oil-soluble (mahogany) sulfonates are equal or superior to those obtained using sulfuric acid or oleum. Schowalter and Lienbacher (i77)secured sulfonate derivatives
September 1950
1747
INDUSTRIAL AND ENGINEERING CHEMISTRY
of aliphatic ketones, possessing useful wetting properties, by reaction of a mixture of aliphatic ketones derived from a C7 to C, paraffin oxidation forerunnings cut with either chlorosulfonic acid or a mixture of acetic anhydride and sulfuric acid in a solvent, such as ether, chloroform, etc. According to a Swiss patent (40) sulfochloroacetic acid is produced in 93 to 95% yield by adding sulfur trioxide to rnonochloroacetic acid at 60" to 70" C.,and heating the mixture a t 140" C. Gonz6les de T h a g o (89) described the synthesis of antipyrene, ephedrine, strychnine, etc., salts of camphorsulfonic acid, which was prepared in good yield by reaction of camphor with a mixture of acetic anhydride and sulfuric acid for 20 days a t room temperature. Products believed to be alkylsulfamic acids, and possessing emulsifying, foaming, and deterging properties, were produced by reaction of urea first with chlorosulfonic acid and then in situ with an aliphatic alcohol containing 10 to 18 carbon atoms General Chemical Division, Allied Chemical and Dye Corporation (76), published a comprehensive summary of literature references disclosing reactions of sulfuric anhydride with aliphatic organic compounds. SULFURYLCHLORIDE,SULFURDIOXIDE-CHLORINE (SULFOCHLORINATION). That sulfochlorination of paraffi hydrocarbons can be effected in the dark with peroxide catalysts waa apparently discovered independently in Germany and the United States. The work of Grubb and Tucker has already been mentioned (194). I n 1944 a t I. G. Wolfen, Weissenborn (207) reported that such sulfochlorinations can be readily effected in an iron reactor having a rough, rather than a smooth surface if 0.03% of a mixture of trimeric acetone peroxide and dihydroxypropyl peroxide (based on the weight of hydrocarbon) be present. He noted that halogen substitution was considerably less in the aforesaid process than in a similar photocatalyzed sulfochlorination. On the other hand, Spaeth (188) found that larger amounts of undesirable unsulfonated chlorinated hydrocarbons resulted when he sulfochlorinated paraffi hydrocarbons in the absence of actinic light but in the presence of one of the catalysts stannic chloride, phosphorus trichloride, sulfur, or kieselguhr containing iron. Asinger (9) continuing studies of products formed in photocatalyzed sulfochlorination of paraffin hydrocarbons of high molecular weight-.& wdodecane-revealed that all methylene groups participate in the reaction equally and to a larger extent than terminal methyl groups. He assumed on the basis of aulfcchlorination of propane and wbutane that the reaction ratio for primary and secondary hydrogen atoms in parafibs of high molecular weight is approximately 1 to 3.25. The original German industrial reports of Asinger and co-workers on identification of products from the sulfochlorination of wbutane (11) and isobutane (10) are noted. Asinger, Eckhardt, and Ebeneder (12) compared the surface-active properties of cetanesulfonates, cetyl sulfates, and cetenesulfonates and concluded that cetanesulfonate obtained by sulfochlorination of cetane was the least desirable. A patent issued to Detrick, Lockwood, and Whitman (48) describes a continuous process for producing polysulfonyl chlorides by treating liquid, saturated aliphatic hydrocarbons with gaseous sulfur dioxide and chlorine. This process is described in detail in the technical section of this review. Helberger, Manecke, and Fischer (87) studied the photocatalyzed sulfochlorination of alkyl chlorides wherein sulfur dioxide and chlorine were introduced in the ratio 1.5 to 2.0 to,1 and reaction was interrupted when approximately 50% of the theoretical amount of chlorine had been absorbed. I n addition to higher chlorinated products, they reported the following: 1-chloropropane gave chiefly 1-chloropropane-2-sulfonylchloride together with a little of the 1,s isomer; 2-chloropropane gave
2-chloropropane-1-sulfonyl chloride; 1-chloro-n-butane gave a mixture consisting of 39% I-chlorobutane-%sulfonyl chloride, 45% 1 , s isomer, and 16% 1,4- isomer; isobutyl chloride gave l-chloro-2-methylpropane-2-sulfonyl chloride; f-chlorohexane gave 1-chlorohexane-&sulfonyl chloride; and 4chloro-&methylpentane gave 4-chlor0-2-methylpentane-2-sulfonylchloride. I n many cases the aforesaid derivatives could not be converted into corresponding sultones by hydrolysis of the sulfonyl chlorides to the sulfonic acid and subsequent dehydrohalogenation. In 1943 at I. G. Wolfen, Brodersen and Quaedvlieg (30) reported that anhydrous aliphatic sulfonates result by reaction of the corresponding sulfonyl chlorides, such as are derived from Mepasin (a hydrogenated Fischer-Tropsch fraction boiling from 220" to 320" C. and containing an average chain length of 15 to 16 carbon atoms), with an aliphatic amide of low molecular weight-e.g. acetamide-together with sodium chloride according to the following equation: RSOzCl
+ CHaCONHz + NaCl --+ CH&N f fCS03Na f 2HC
The by-product acetonitrile can be recycled with hydrochloric acid to acetamide, so that, in effect, sulfonyl chlorides are converted to anhydrous sulfonates solely with sodium chloride. At the same time they revealed that an even better process comprises reaction of the sulfonyl chloride with the sodium salt of a low molecular weight aliphatic acid according to the equation :
ItSO&l
+ R'COONa +R'COCI + RSO3Na
The by-product aliphatic acid chloride can be recycled to its acid salt for re-use. According to a British patent (179) crude alkylsulfonate mixtures containing, for example, 82.6 parts of n-paraffinsulfonates containing 14 to 15 carbon atoms, 18.6 parts of alkanes ("unsaponifiable elements"), 19.6 parts of sodium chloride, and 60 parts of water, yield alkylsulfonate products virtually free from the afore-mentioned impurities by a two-stage proceM comprising (1) chlling the crude mixture at 0" C. and filtering off most of the sodium chloride together with the solid fraction of alkanes, and (2) passing the filtrate over rollers heated to about 150' C. to evaporate water and the remaining alkanes. German information on sulfochlorination of aliphatic hydrccarbons during the period 1939 to 1946 has been reviewed (176). SULFURDIOXIDEAND OXYQEN. An I. G. Farbenindustrie industrial report (98) presents a comprehensive account of the sulfo-oxidation reaction mechanism of n-heptane, cyclohexane, and methylcyclohexane. ! Substitution or Addition Reactions with Sulfites and Bisulfites. In connection with a study of alkenesulfonic acids, Lambert and Rose (119) synthesized sodium 2-hydroxy-2-methyl-1-propanesulfonate from 1,2-dibromo-2-methylpropaneand aqueous sodium sulfite, and sodium %hydroxy-1-propanesulfonate from propylene oxide and aqueous sodium bisulfite. According to a British patent (66),an improved process for preparing salts of chloroethanesulfonic acid in 80 to 90% yield comprises heating at atmospheric or slightly higher pressure a mixture of dichloroethane and an aqueous solution of an alkali or an alkaline earth metal sulfite. The process is said to make unnecessary the use of a solvent such as methyl or ethyl alcohol, and to effect a more rapid reaction with higher yield than when such a solvent is employed. I6
6
..
...
280
6
..
...
260
.
.
I
HzO
20
..
., .. .. ..
..
..
15
..
..
80 80 98 50
..
..
..
35 75-80 >75-80
..
..
...
... ...
... ...
...
.
.
.
(SO%?
...
..
..
..
6
..
.. .,
..
98
...
..
..
...
..
...
..
..
...
...
..
sulfonate derivatives which possess surface-active properties superior to those derived from polybutylenes of similar chain length. Weinmayr (206) disclosed that compounds, such as sodium-2-methyl-2-phenyldecanesulfonate,which contain a sulfonated benzene ring attached to the tertiary carbon atom of a 2-methyl-n-alkane having a total of 10 to 14 carbon atoms, are outstanding deterging and wetting agents. Weinmayr and coworkers (99-94)patented related products having the following structures : H HG-&-R H
RX-4-+Rf‘ X-
(1)
I
-R’
- - -R” R/!f
(11)
R and R’ straighhchain a]kyl radical of 5 to 6 carbon atoms each R” and R”’ = hydrogen or methyl X = sulfonic acid radical or salt thereof i .
Compounds of Type I are said to possess outstanding detergent power a t low concentrations in hard water, and those of Type I1 outstanding wetting properties. Smith, Crowley, and Waldo (186) found that the wetting power of monoalkyl aryl sulfonates can be improved by admixing a t least one di- or trialkyl aryl sillfonate having a total of 9 to 27 carbon atoms in the alkyl groupse.g., sodium diheptylbenzenesulfonate, sodium tert-butyldecylbenzenesulfonate, etc. Flett (64-66) reported that the following classes of compounds inhibit the formation of rancid odors in drum-dried, mixed alkyl aryl sulfonates which are derived from petroleum distillates and are suitable for wetting, emulsifying, or deterging operations: (I) aromatic amino compounds containing less than 11 nuclear carbon atoms per aromatic nucleus-e.g. , benzidine, isopropoxy-
... ...
... ... ...
Anthra ‘uinone
290
..
...
... ... ...
.. ..
...... ......
...
.
..
260
...
. I . I
,.
6.5
Hydroxysulfonie acid first appears at 260’ C.
...
...
... ... ... ... ...
Remarks 2-Isomer first appears at 260” C.
... ... I
30:(2’,7)
...
...
hydrocarbon of 8 to 11 carbon atoms R’ = methyl or ethyl, but hydrogen if R” is methyl R” = methyl, but hydrogen if R’ is methyl or ethyl X = sulfonic acid radical or salt thereof
30
.. .. .. .. .. ..
.. .. .. 45-(2,6) ...
...
... ,..
R = straight-chain saturated
.. ..
260
Ha0
Y
.... .... .. .. ..
...
.. .. *.
0.25% Hz604 TO80% &SO4
k
. .6.
230 230
Hz0 Hz0 Much HzO
Miscellaneous Including ecovery)
290 260
290 290 290
1,6-Isomer
l,.i-Isomer
Hydrolysis
Vol. 42, No, 9
... ...
... 1 8-Dihydroxybnd l-hydroxyanthraquinones (total 48%)
40 co.
HsO pir 0.04 mole
disulfo
...
... All possible hydrolysis products Either or both sulfo groups replaced by H or OH
diphenylamine, di-ptolylthiourea, etc.; (2) nonbenzenoid antoxidants-e.g., geraniol, camphor, dodecylamine, fumaric, maleic, tartaric, and aspartic acids, etc.; and (3) heterocyclic compounds-e.g., coumarin, isatin, antipyrene, benzotriazole, etc., and particularly those with a critical oxidation potential of about 0.8 volt. Several Swiss patents disclose new surface-active compounds, which are aryl sulfonate products containing a relatively long side chain derived from fatty acids, and which may also contain other nuclear substituents. These sulfonates are prepared by (1) condensing a fatty acid or its derivative (such as an acid chloride or amide) with an aromatic compound (such as an arylhydrazine or phenol) and then sulfonating the condensation product, or (2) simultaneously condensing and sulfonating a fatty acid derivative and an aromatic compound with a sulfonating agent-e.g., sulfuric acid or oleum. The afore-mentioned compounds comprise sulfonate derivatives of the following: palm kernel fatty acid hydrazides (67, 68, 7%76), N-(ptolyIsulfony1) octadecenyl (-p)aniline (70), and products obtained by condensing stearic acid amide with cup’-dichlorodimethyl ether and then with phenol (38)or with anisole (39). According to Shuck and Lingafelter (181) a mixture of triisopropylbenzenesulfonic acids, which are colloidal electrolytes with critical concentrations at 0.055 M (acids) and 0 063 M (sodium salts), ww prepared by reaction of either tri- (chiefly 1,2,4-) or tetrapropylbenaenes with 15% oleum in carbon tetrachloride. Engelbertz and Klornorr (63) investigated the production of 5-hydrindenesulfonic acid by sulfonation of hydrindene. They obtained the following mixtures of the 4- and 5-sulfonic acids, respectively (from which the 5- isomer was separated in pure form by appropriate dilution of the reaction mixture): 29 and 71% (at 90”to 95” C. with sulfuric acid), 18 and 82% (at -10” C. with oleum), and 12 and 88% (with chlorosulfonic acid in carbon tetrachloride). At the same time they disclosed a sulfonation method for separating a mixture of 4- and 5-chlorohydrindenes, Thus, they treated a mixture of 35% 4 and 65% 5-chlorohydrindenes with 90% sulfuric acid and found that after separating the sulfonic acids, 60% of the bchlorohydrindene present in the mixture remained behind unsulfonated. Indirect Sulfonation. Miller et al. (186) synthesized 4-amino-2-
INDUSTRIAL AND ENGINEERING CHEMISTRY
(September 1950
*
nitrobenzenesulfonic acid in 45% yield from m-dinitrobenzene and aqueous sodium bisulfite. They found that the 4amino-2hydroxybenzenesulfonic acid obtained therefrom ww identical with one of uncertain structure obtained by heating m-aminophenol with 3 parts of concentrated sulfuric acid on the water bath for 1 hour (identified by a mixed melting point study of the pyridinium Cacetylamino-Zac e t o x y b e n z e n e s u If o n a t e d e rivatives). Russian investigator8 (18, 19,801-804) reported studies of the reaction of bisulfites with quinones, quinone derivatives, mixtures of quinones and aromatic amines, and azo cohpounds. Ufimtsev (8Oi-804) disclosed the following such bisulfite reactions. Resorcinol gave trisodium l,3-dihydroxy-1,3,5cyclohexanetrisulfonate (I) decomposed by alkali to yield sodium m-phenolsulfonate. A mixture of resorcinol or I and pphenylenediamine formed sodium 1,3-bis(paminoanilino)-dihydro-&benzenesulfonate (801). Chrysoidine gave a bisulfite adduct which has the probable structure:
1755
produced by reacting the respective l-amino-2,4dihalogen0-6(or 7)-anthraquinonemonosulfonic acids first with a nuclearly substituted aniline and then with aqueous alkali sulfite (169174). Anthraquinone dyestuffs of similar constitution but containing in the 4- position a halogen-free hydroarylamino group, such as a cyclohexylarnino group, are said to dye wool and nylon beautiful blue shades of great purity and excellent fsstness to light (7). According to an I. G. Farbenindustrie patent application (97) sultones, such as o-tolylsultone and Gvalerosultone, react with organic compounds containing an amino or hydroxyl group to yield sulfonic acid derivatives as shown by the following equations :
CHI(CH~)LT NHCH~C~HISO~H
and is said to differ from known bisulfite compounds of other azo dyes by virtue of its poor solubility in water and dilute acids and its content of an NHZ group instead of an OH group. The adduct was decomposed by dilute alkali to regenerate chrysoidine and unidentified water-soluble products ($09). 1,4Naphthoquinone gave 1,4dihydro-1,4-dihydroxy-l,4naphthalene disulfonate which is decomposed by alkali to give 1,4naphthoquinone and 1,3-diketo-2-hydrindenesulfonate (804). The methylphenylhydrazone of 1,4naphthoquinone gave 1-(methylphenylhydrazono) 4 hydroxy 1,4 dihydro 4 naphthalenesulfonic acid (stable in water or dilute acid solution but rapidly transformed to the original hydrazone by cold alkalies or carbonates) (803). Bochvar e l aZ. (19) disputed Ufimtsev's structure of the bisulfite addition product of 1,4-naphthoquinone. They found it to be an adduct containing an oxo radical in the 4 position and a hydroxy group in the 1- position. Ab the same time they stated that bisulfite addition compounds of pquinones are of three types: (1) a complex which shows resonance and cannot react with hydrazines without splitting; (2) an adduct, which is formed from the complex, and which yields a hydrazone if it contains a CO group; and (3) a hydroquinonesulfonate, which is formed from the adduct and which cannot give a hydrazone (19). Bochvar et al. (18) produced d y e s t d s by coupling bisulfite adducts of 1,4naphthoquinone or 1-nitroso-2-naphthol with diazo compounds, such as pdiazonitrobenzene and pdiazobenzenesulfonic acid. Bock and Rainey (20) discovered that macromolecules of the following structure
- -
- -
- -
Oxidation of Sulfur Compounds. Witte and Welae (215, 21.4) patented a process for mbufacturing pnitrobenzene&lfonyl chloride in Bo to 65% yield, which comprises oxidizing di-pnitrophenyl disulfide with a mixture containing nitric acid and chlorions and an inert immiscible solvent, such as petroleum ether, which preferably dissolves the sulfonyl chloride but not the disulfide. When the oxidizing agent is a mixture of nitric 8nd hydrochloric acids, the over-all reaction is believed to take place according to the following equation : 3NOzCeH8SCdI4NOz
+ lO"01
+
6HCl + 6NO&sH&302Cl lONO
+
+ 8Hz0
Hartmann (86) oxidized o-nitrodisulfides comprising the following structures:
X = H, CHs, C1, and OCHs R = alkyl or aryl with chlorine in aqueous hydrochloric acid to yield corresponding sulfonyl chloride derivatives, which are valuable intermediates in the manufacture of dyestuffs, yielding reddish shades of great light fastness and resistance to peroxide. In connection with a study of the thionaphthene derivatives, Challenger and Clapham (86) oxidized a nitrothianaphthene sulfone with potassium permanganate to produce 4nitro-2-sulfobenzoic acid in 76% yield, and deduced thereby that the starting compound was Bnitrothianaphthene sulfone. HETEROCYCLIC
It = an alkylene group R' hydrocarbon substituent of a t least four carbon atoms x = integer > 1 =i
y
N
= zero or integer between 1and 20 =
one equivalent of a metal
exhibit surface-active properties, which are not dependent on the formation of micelles. The macromolecular sulfonates were secured by heating the corresponding halogen compound with an aqueous or aqueous-alcoholic sulfite solution. l-hmino-4-anilino-2,&(or 2,7)-anthraquinonedisulfonic acids, which are dyestuffs for wool, silk, and nylon-type fibers, were
Wendland, Smith, and Muraca (208, 909) prepared Zdibenzofuransulfonic acid in 75% yield by heating a mixture of dibensofuran and concentrated sulfuric acid a t 100" C. for 1hour. They reported that the afore-mentioned sulfonic acid melts sharply a t 147-147.5' C. (rare for a sulfonic acid to have a sharp melting point). It appears to be a precipitant for metal ions and has particular promise aa an analytical reagent for lithium, sodium, and potassium ions. Bergdolt and Schmelzer (14) prepared the difficultly obtainable o-monosulfonic acid derivatives of 2hydroxycarbazole and 2-hydroxydibenzofuran in about 60% yields by reaction of the latter compounds with sodium chlorosulfonate in the presence of a solvent. It is noteworthy and surprising that only one solvent worked in each case: ethyl acetate for 2-hydroxycarbazole and chlorobenzene for 2-hydrosy-
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
1756
dibenzofuran. Borodkin and Mal'kova (86) investigated the hydrolysis of 3-carbazolsulfonic acid in aqueous sulfuric and hydrochloric acids--e.g., 100% hydrolysis by heating with 5% hydrochloric acid 4 hours at 160' in a sealed tube, 81 % hydrolysis by refluxing 12 hours in 45% sulfuric acid, etc. They (35) also reported synthesis of 1,3,6-rarbazoletrisulfonic acid by reaction of carbazole with 67 to 100% sulfuric acid at 90" to 115' C., or with concentrated sulfuric acid and oleum, in two stages, a t 90' to 100' C. They identified the acid by comparing it with the trisulfonic acid secured by deaminating 2-amino3,6,&carbazoletrisulfonic acid. HYDROCARBON STORAGE TANK
FLOW METER UPPERLEVEL REACTION MASS
POROUS BLOCK 5O2tCL2
2
AS CHAMBER
Vol. 42, No. 9
Bridgwater, and Axelrod (89) synthesized barium salts of dZhexahydro-Zoxo-1-fur~(3,4)-imidaaole-P(Pbutanesulfonic acid) (sulfonic acid analog of dl-oxybiotin) and dl-hexahydro-2-oxo-lfuro-(3,4)-imidazole-4(E-pentanesulfonic acid) (sulfonic acid analog of dl-homo-oxybiotin) by oxidation of the corresponding mercaptans with barium permanganate in aqueous solution. They reported microbiological activity of these sulfonates and other related compounds against Lactobacillus arabinosus and Saccharomyces cereuisiue test organisms. The first mentioned sulfonate, like dZ-homo-oxybiotin, antagonizes the growthpromoting activity of d-biotin and dl-oxybiotin, whereas the last mentioned sulfonate, unlike dl-homo-oxybiotin, possesses a growth-stimulating activity for the test organisms. Mechanism and Kinetics. Crooks (45) presents a detailed report of a comprehensive investigation of the rate of sulfonation of benzene by benzene-saturated sulfuric acid solutions over a temperature range from 90" to 140" C. where 0.239 to 15.81 moles of benzenemonosulfonic acid were formed per hour per liter of solution. He discovered that the specific reaction rate at atmospheric pressure is an exponential function of the solution composition and a logarithmic function of the absolute temperature according to the following equation:
k
GAS INLE? PIPE
Figure 1.
Reactor
According to a British patent (151) monosulfonic acid derivatives of pyridine and 3-alkylpyridines can be obtained in 21 to 63% yields by heating a t 180e to 200' C. a mixture of the corresponding pyridiniumsulfonic acid and sulfuric acid in the presence of a catalyst, such as the sulfate of mercury, vanadium, aluminum, or magnesium. In connection with a study of sulfanilamide derivatives of coumarin, Fedosova and Magidson (69) reported the preparation of 3-acetamido-6-coumarinsulfonyl chloride in 50.5% yield by reaction of Bacetamidocoumarin with chlorosulfonic acid a t 60" to 65" C. Bindler and J R. Geigy A. G. (15, 69) discovered that guanamines of high molecular weight such as are formed by heating stearoylxylylbiguanide a t 190' to 200' C., react with oleum to yield sulfonic acid derivatives, which possess capillary-active properties and serve &s stripping or leveling agents in vat dyeing, and aa softening agents, water-fastness improvers, etc. Water-soluble sulfonates of benzimidazoles possessing blue to violet fluorescence, useful in whitening textile materials, etc , are secured by sulfonating a,&di- [benzimidazolyl-(2)]-ethylene and similar compounds with oleum (85). According to a Swiss patent (71) azo dyestuffs which impart lightfast yellow shades to cellulose are prepared by first oxidizing a Zaminophenylbenaothiazole, such as dihydrothio-m-xylidine, with sodium hypochlorite and then sulfonating the resulting product with oleum. Gutzwiller (85) produced sulfonate derivatives of some arylthioethers of phthalocyanines by sulfonating symmetrical tetrathiophenoxy, tetra-p-thiocresoxy, and tetrathionaphthoxy copper phthalocyanine, and similar compounds, with sulfuric acid, oleum, or chlorosulfonic acid in the presence or absence of a solvent such as dichlorobenzene. The sulfonates are wa,tersoluble dyestuffs dyeing cotton, silk, and paper bluish green to yellow-green shades of great brilliancy and extraordinary fastness to light. Wieland, Fischer, and Moewus ($10) found that sodium &skatylsulfonate, which unlike bindoleacetic acid inhibits root growth of Lepidium sativun, can be prepared in 57% yield by heating a mixture of a-dimethylaminoskatole, sodium bisulfite, and aqueous methanol a t 100" C. under pressure for 5 days In connection with studies on the chemical structure and biological activity in the biotin and oxybiotin series, Hofmann,
RL XA Xw Xs
T
CA
= rate of benzene sulfonation, moles of benaenesulfonic
acid/(hour) (liter) mole fraction sulfuric acid. benzene-free basis in sulfonation = mole fraction water = mole fraction benzenesulfonic acid benzene-free basis = absolute temperature, degrees Kedin = concentration of sulfuric acid, mole/liter =
Brand and Rutherford ( 8 7 )studied the kinetics of the reaction between oleum and ( 1) p-nitrotoluene to give 4-nitrotoluene-2sulfonic acid, (2) p-toluyitrimethylammonium methosulfate to give p-toluyltrimethylammonium-2-sulfonate,and (3) phenyltrimethylammonium methosulfate to give phenyltrimethylammonium-3-suIfonate in 80% yield together with 12% of the 2- isomer and 87" of the 4-isomer. They believe that sulfonation in oleum is a further example of the type of substitution where group X is inscrted by reaction of the aromatic system with the cation X + , as already proposed by Hinshelwood et al. (1.84, 1g6) for the reaction in nitrobenzene. Shilov and Kurakin (180) challenged Alexander's views (1.84, 185) concerning the mechanism of sulfonation of aromatic amines on the basis of Kurakin's report (118) that a mixture of about equal amounts of m- and p-dimethylanilinesulfonic acids is obtained by sulfonation of dimethylaniline with oleum. Alexander founded his hypothesis, in part, on a prior literature report that m-dimethylanilinesulfonic acid is the sole isomer formed by the interaction of oleum and dimethylaniline a t 55' to 60' C. They explain the formation of both p - and m- isomers by the presence of free amine, which is para-directing, and ammonium salt, which is meta-direrting, according to the equilibrium reaction:
CeHjN(CHa)2
+ H2SOd
[CIHSN(CHI)~H]~[~O~]-
They further postulate that in the sulfonation of primary and secondary amines, the meta isomers are likewise formed through the ammonium form, whereas the ortho and para isomers are formed via the free amine and the sulfamic acids. Lulrin (137) interprets the behavior of sulfuric acid in SUIfonation reactions on the basis of two reactive species: (1) H 2 0 SO3, predominating in concentrated solutions and particularly at high temperatures, and (2) H +S04H-, predominating at lower concentrations and especially a t lower temperatures. Thus, in the case of polycyclic ketones, on which the interpret& tion is founded, reaction with concentrated sulfuric acid gave
INDUSTRIAL AND EPGINEERING CHEMISTRY
September 1950
&onoxide intermediates which On further reaction resulted in sulfonic acid derivatives according t o the following scheme:
R'
)c R.
R' 0 4-
H&.sos e )c
= ~ . S O S4- H * O q sulfonicacid
whereas reaction with dilute sulfuric acid formed sulfate derivativea incapable of forming sulfonic acids on further heating. He alleges that easily sulfonatable compounds Possessing strongly Dolar substituents such aa Dhenof are sulfonated bv the sDecies k+so,~-,but that sulfonations Occur th;.ough - i n h mediates (not investigated) other than sulfonoxides. Identification and Analysis of SulfonicAcids. 8-1-Naphthdmethylthiuronium chloride (like its predecessors Sbenzylthiuronium-chloride and 8-p-chloro- and k-pbromobenzylthiuronium Chlorides) reacts practically quantitatively with organic sulfonic acids to give salts, which are eesily purified by crystallization, and possess sharp melting points ($9)Gillman and Abbott (78) have extended the thallous salt method for characterizing sulfonic acids (by melting point) to arylsullinic and other acids. They note that the method is leas Satisfactory with alkyl sulfonates than with aryl sulfonates. Borodkin and Mal'kova (94)selectively precipitated the benzidine salt of 2,3,6,&arbazoletetrasulfonic acid from a mixture of isomeric acids and estimated it by alkimetric titration. Mercier (134) reported that potassium ferrocyanide is not a satisfactory reagent for characterizing camphorsulfonic acid. In the estimation of cationic and anionic surface-active agents by simple titration procedures, Barr, Oliver, and Stubbings (13) found that end points can be determined with good accurwy if the titration is carried out in the presence of an organic solvent -e.g., chloroform-and the indicator is methylene blue for anionic agents and bromophenol blue for cationic agents. Salton and Alexander (166)discovered that pinacyanol bromide is an excellent indicator for judging the end point in the titration of a cationic with an anionic detergent to form an insoluble precipitate-for example, when 0.0025 N dioctylsulfosuccinate is titrated with cetyltrimethylammonium bromide of about the same strength, 0.1 ml. of 0.05% pinacyanol bromide is recommended (accuracy 1%). Standard analytical methods employed by I. G. Farbenindustrie A*-G. for intermediates including many sulfonic acids are noted (99, 101-103).
TECHNICAL DEVELOPMENTS ALlPHAllC
Detrick, Lockwood, and Whitman (48) disclose a continuous process for producing aliphatic polysulfonyl chlorides, which may be performed in the apparatus shown in Figures 1 and 2 (one modification of the disclosure). An outstanding feature of this apparatus is that it avoids a separation of the reaction m m into immiscible phases, which seriously decreases the efficiency of the reac tion. The reactor (see Figure 1) is made up of a horizontal tank which is divided into two horizontal sections by a ceramic porous block
partition. The lower section is divided into four chambers, each provided with a gas inlet pipe, to facilitate regulation of the introduction of gas through the porous block partition. The upper section is divided into seven vertical zones by baffles, which extend from the surface of the porous block to the ceiling of the tank. Along a side of each baffle is a narrow slot or opening, which is situated below the intended level of the liquid reaction mass, and is arranged 80 that successive baflles carry the slots on ppposite sides, thus providing a eta gered arrangement of openAs illustrated in Figure 2, eack zone haa a cooling coil and well containing a fluorescent lam which emits light of 3000 to 6000 A. The reactor is provided wit1 a feed pipe for introducing hydrocarbon into the inlet zone and a ipe for discharging reaction mixture from the outlet zone, as w e l a s pipes for ventin? each of the zones. The reactor shell, which is 6 inches wide, 33 inches long, and 12 inches deep, is constructed of steel having an inner
;i"yi
1751
lead lining which in turn is coated with porcelain brick set in acidproof cement. The baffles, light wells, and cooling coils are made of borosilicate nlass. In operation; a saturated hydrocarbon fraction-e.g., boilin range 263" to 305" C., specific gravity 0.801 a t 15.1' C.-is fed continously into the inlet zone of the reactor a t the rate of 58 pounds per hour, passes through the successive zdnes via the slot openings in the baffles, and leaves the reactor through the product dischafge Pi SimultaneOuslY, a gaseous mixture Of 14.6 pounds of sulf$ dioxide and 12 unds of chlorine per hour is continuously introduced through porous block floor into the reaction zones. from which the reaction eases are discharaed throuzh the vent Dioes. The reaction mass ismaintained a t 25' to 30'c. througho;t^ by circulating water through the coils. The effluent reaction mass consistin of a mixture of hydrocarbon sulfon 1 chlorides and unreactet hydrocarbons, and having a specitc gravity of 0.940 a t 30° C.,. is produced a t the rate of 77 pounds per hour.
te
UGHT WELL
7rFLWRESCENt L A W
coot
REKTION
-POROUS 81LOCK
CAS CHAMBER
Figure 9. Apparetuc for Producing Aliph4tic Polysulfonyl Chlorides
In an excellent review of German synthetic detergent developments, Hoyt (90) reports manufacturing details for the commercial production of sodium isethionate from ethylene oxide and aqueous sodium bisulfite, and methyl taurine from sodium isethionate and methylamine. These sulfonates were required for the manufacture of Igepons a t I. G. Hoechsb-e.g., Igepon AP Extra Concentrated from oleyl chloride and sodium isethionate. Proell (160) patented a catalytic oxidation process for the commercial production of lower alkanesulfonic acids in equipment exceeding laboratory scale. This process is discussed in the theoretical section of this review under the heading "Oxidation of Sulfur Compounds." AROMATIC
Governmental publications dealing with German chemical industrial operations reveal detailed information concerning many technical sulfonation methods (100, f04-108). It is beyond the scope of this review to evaluate the numerous methods discussed in such publications. Two of the afore-mentioned publications (100, 106) are noteworthy because they disclose processes written or revised after 1940. Hunt (91) reported that a violent explosion occurred at the Du Pont Chambers Works, Deepwater Point, N. J., while lo00 pounds of pnitrotoluene were being dissolved in 3995 pounds of 93% sulfuric acid in a 5OO-gallon jacketed kettle. Accidental overheating of the charge beyond the normal dissolving temperature of 80' C. is believed to have initiated the explosion. A study showed that heating a solution of pnitrotoluene and sulfuric acid to 160' C. initiates an exothermic reaction which results in an explosion, Spryskov (193) and Wmkelmueller (9f1 ) suggest that laboratory processes which they developed for preparing benzenemonosulfonic wid offer advantages for oommercial application. Cas-
INDUSTRIAL AND ENGINEERING CHEMISTRY
1758
per and Petzold’s coniprehensive laboratory study of the sulfonation of aromatic amines by the so-called baking process in indifferent solvents is designed to overcome difficulties and to iaprove operation of the process on a commercial scale ($5). Numerous other references disclosing sulfonation methods and /or sulfonate products of technical interest are described in the theoretical section of this paper. To avoid undue repetition, they are not presented here.
ACKNOWLEDGMENT The writer wishes to express his appreciation t o various members of the staff of National Aniline Division, Allied Chemical and Dye Corporation, for cooperation in the preparation of this review and in particular t o A. Victor Erkkila for considerable aid in its preparation, to Samuel M. Lazarus, Theodore Mariam, Irving Thornton, and others for translations and suggestions, and to Bradley Woods for the drawings. CORRECTION§ I n the review of sulfonation published in 1949 (186) reference (144) should read U. S. Patent 2,448,184 (Aug. 31, 1948); reference (51) on page 1925, first column, 17th line from bottom of page, should refer to 2butoxy-5aminopyrimidine instead of Zbutoxy-Saminopyridine. LITERATURE CITED (1) Abrahamson, B., Lindgren, B. O., and Hagglund, E., Suensk Papperstidn., 51, 471-4 (1948). (2) Adams, H., and Briggs, G. H., Ltd., Brit. Patent 621,618 (April 13, 1949). (3) Adama, R., and Garber, J. D., J . Am. Chem. SOC.,71, 522-6 (1949). (4) Adams, R.,and Lipscomb, R. D., Zbid., 71,519-22 (1949). (5) Aktien-Gesellschaft vorm. B. Siegfried, Swiss Patent 242,286 (Sept, 16, 1946). (6) Allen, C. F. H., and Burness, D. M., J. OVJ. Chem., 14, 163-9 (1949). (7) Allmen, S. v., and Eggenberger, H. (to Sandos Ltd.), U. S. Patent 2,453,285 (Nov. 9, 1948). (8) Arnold, M. H. M., and Perry, W. E. (to Imperial Chemical Industries, Ltd.), Zbid., 2,471,018 (May 24, 1949). (9) Asinger, F., U. S. Dept. Commerce, OTS Rept., PB 70428, FIAT Microfilm Reel E-25, Frame 8090 (April 1944). (10) Asinger, F., and Ebeneder, F., Zbid., PB 857, Rept. 317 (-4pril 1942). (11) Asinger, F., Ebeneder, F., and Bock, E., Ibid., PB 849, Repf. 26 (April 1941). (12) Asinger, F., Eckhardt, and Ebeneder, F., ZW., 70183, FIAT Microfilm Reel 0-43, Frames 840-9 (February 1941). (13) Barr, T., Oliver, J., and Stubbings, W. V., J . SOC. Chem. 2nd. (London),67,45-8 (1948). (14) Bergdolt and Schmelser, U. 5. Dept. Commerce, OTS Rept., PB 75431, Enlargement Print of Frames 2779-82 of FIAT Microfilm Reel C 61, PB 17658 (March 1936). (15) Bindler, J. (to J. R. Geigy A. G.), U. S. Patent 2,451,432 (Oct. 12, 1948). (16) Bissinger, W. E., Kung, F. E., and Hamilton, C. W., J . .4m. Chem. SOC., 70,3940-1 (1948). (17) Blangey, L., and Fierr-David, H. E., Helv. Chim. Acta, 32, 631-4 (1949). (18) Bochvar, D. A., Levitskaya, S. V., and Shemyakin, h i . M., Doklady Akad. Nauk S.S.S.R.,50, 197-8 (1945). (19) Bochvar, D. A., Vinogradova, E. I., Shvetsov, Y. B., and Shemyakin, M. M., J . Gen. Chem, (U.S.S.R.), 18, 87-97 (1948). (20) Bock, L. H., and Rainey, J. I,. (to Rohm & Haas Co.), U. S. Patent 2,454,543 (Nov. 23, 1948). (21) Ibid., 2,454,546 (Nov. 23, 1948). (22) Bonner, W. A., J . Am. Chem. SOC.,70,3508-9 (1945). (23) Bordwell, F. G., and Rondestvedt, C. S., Jr., Zbid., 70, 2429-33 (1948). \----I
(24) Borodkin, V. F., and Mal’kova, T. V., J . Applied Chem. (U.S.S.R.), 21, 171-2 (1948). (25) Ibid., pp. 849-53. (26) Ibid., pp. 1032-6. (27) Brand, J. C. D., and Rutherford, A., Research (London), 2, 195-6 (1949). (28) British Celanese, Ltd., Brit. Patent 625,757 (July 4, 1949). (29) Brodersen, U. S. Dept. Commerce, PB Rept. 70346, FIAT Microfdm Reel C-17, Frames 19673-7 (July 5, 1933).
Vol. 42, No. 9
(30) Brodersenand Quaedvlieg,Ibid., PB843, Rept. 207 (May 5,1943). (31) Bryde, @., Finnish Paper Timber J., 29, 296-301, 317-23 (1947). (32) Burton, H., and Hu, P. F., J . Chem. Soe., 1948, 604-5. (33) Eurwell, R. L., Jr., and Gordon, G. S., 111, J . Am. Chem. Soe., 70, 3128-32 (1948). (34) Caldwell, J. R. (to Eastman Kodak Co.), U. S. Patent 2,478,368 (Aug. 9, 1949). (35) Casper and Petrold, U. S. Dept. Commerce, P B Rept. 73911, FIAT Microfilm Reel N87, Frames 4648-60 (March 10, 1933). (36) Challenger, F., and Clapham, P. H., J. Chem. SOC.,1948, 161518.
(37) CIBA Ltd., Swiss Patent 224,118 (Feb. 1, 1943). (38) Ibid., 224,858 (March 16, 1943). (39) Zbid.,224,860 (March 16, 1943). (40) Zb{d., 231,254 (June 1, 1944). (41) Ibid., 233,844 (Dec. 1, 1944). (42) Ibid., 248,688 (Feb. 16, 1948). (43) Claus, A., and Bopp, H., Ann., 265, 96-107 (1891). (44) Conn, R. C., and Weiss, R. H. (to American Cyanamid Co.), U. S. Patent 2,471,400 (May 31, 1949). (45) Crooks, R. C., Pub. 1181, Ann Arbor, Mich., University Microfilms, 1949. (46) Culvenor, C. C. J., Davies, W., and Heath, N. S., J . Chen. SOC., 1949, 278-82. (47) Delfs, D., “FIAT Review of German Science 1939-1946. Preparative Organic Chemistry,” Part I, Karl Ziegler, senior author, p. 254, Wiesbaden, Office of Military Government for Germany Field Information Agencies Technical (British, French, and U. 5. A.), 1948. (48) Detriok, S. R., Lockwood, W. H., and Whitman, N. (to E. I. du Pont de Nemours & Co.), U. 5. Patent 2,462,730 (Feb. 22, 1949). (49) Dice, J. R., and Smith, P. A. S., J . Org. Chem., 14, 179-83 (1949). (50) Diotti, G., Italian Patent 422,330 (June 13, 1947). (51) Doering, W. von E., and Beringer, F. M., J . Am. Chem. Soc., 71, 2221-6 (1949). (52) Eikhman, R. K., and Bogdanov, M. I., Anilinokrasochnaya Prom., 4, 396405 (1934). (53) Engelberts, P., and Klornorr, B., U. S. Dept. Commerce, PB Rept. 75323, Enlargement Print of Frames 2210-13 of FI.4T Microfilm Reel C61, PB 17658 (April 1935). (54) Erdtman, H., Tappi, 32,346-8 (1949). (55) fitatfrancais, Brit. Patent 605,973 (Aug. 4, 1948). (56) fitienne, A., and Heymbs, R., Compt. rend., 227, 1252-4 (1945). (57) &tienne, A., Lepeloy, J., and Heymbs, R., Bull. SOC. chim. France, 1949, 83540. (58) Ettel, V., and Weichet, J., Collection Czechoslou. Chem. Corn muns., 13, 433-41 (1948). (59) Fedosova, V. M., and Magidson, 0. Y., J . Gen. Chem. (U.S.S. R.),18, 1459-66 (1948). (60) Fischer, Kissling, and Kracker, U. S. Dept. Commerce, PB Rept. 17679, FIAT Miarofilm Reel C91, Frames 3350-3 (Feb. 25, 1930). (61) Fitsky and Cramer, Zbid., 58818, Enlargement Print of Frames 644-5 of FIAT Microfilm Reel C28, PB 14998 (April 27, 1938). (62) Fleischhauer, R., and Mueller, A., Zbid., 73494, FIAT Microfilm Reel C-6, Frames 6876-81 (Nov. 10, 1937); German Patent 706,836 (June 6, 1941). (63) Flett, L. H. (to Allied Chemical & Dye Corp.), U. S. Patent 2,452,043 (Oct. 26, 1948). (64)Zbid., 2,469,376 (May 10, 1949). (65) Zbid., 2,469,377 (May 10, 1949). (66) Ibid., 2,469,378 (May 10, 1949). (67) Geigy, J. R., A. G., Swiss Patent 217,226 (Feb. 2, 1942). (68) Zbid., 220,926 (Aug. 1, 1942). (69) Zbid., 220,930 (Aug. 1, 1942). (70) Ibid., 227,071 (Aug. 2, 1943). (71) Ibid., 239,006 (Dec. 3, 1945). (72) Ibid., 242,985 (Nov. 1, 1946). (73) Zbid., 242,986 (Nov. 1, 1946). (74) Ibid.. 243.098 (Nov. 16. 1946). (75) 2bid.l 244;579 iMay 1, 1947). (76) General Chemical Division, Allied Chemical & Dye Corp., Tech. Service BUZZ. SF-2(1948). (77) Gilbert, G. R. (to Standard Oil Development Co.), U. S. Patent 2,485,721 (Nov. 22, 1949). (78) Gilman, H., and Abbott, R. K., Jr., J . Am. Chem. Soe., 71, 659-60 (1949). (79) Gold, M. H., and Druker, L.J. (to Visking Corp.), U. S. Patent 2,477,869 (Aug. 2, 1949). (80) Ibid., 2,477,870 (Aug. 2, 1949).
September 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
(81) Goll, U. S. Dept. Commerce, PB Rept. 73893, FIAT Microfilm
Reel N-77, Frames 6206-9a (April 23, 1938). (82) Gonzhlez de TBnago, J., Anales real acad. farm., 9, 235-58 (1943). (83) Granacher, C., and Ackermann, 3’. (to CIBA Ltd.), U. S. Patent 2,463,264 (March 1, 1949). (84) Grotowsky, U. S. Dept. Commerce, OTS Rept., PB 75372, Enlargment Print of Frames 2124-5 of FIAT Microfilm Reel C61, PB 17658 (March 25, 1935). (85) Gutzwiller, E. (to Sandoz, Ltd.), U. S. Patent 2,465,089,(March 22, 1949). (86) Hartmann, E., U. S. Dept. Commerce, OTS Rept., PB 75421, Enlargement Print of Frames 2713-14 of FI.4‘r Microfilm Reel C61, PB 17658. (87) Helberger, J. H., Manecke, G., and Fischer, H. M., Ann., 562, 23-35 (1949). (88) Hinze, U. S. Dept. Commerce, OTS Rept., PB 73616, FIAT Microfilm Reel M106, Frames 1471-3 (Aug. 30,1945). (89) Hofmann, K., Bridgwater, A., and Axelrod, A. E., J . Am. Chem. SOC.,71, 1253-7 (1949). (90) Hoyt, L. F., U. S. Dept. Commerce, OTS Rept., PB 3868 (1945). (91) Hunt, J. K., C h m . Eng. News, 27,2504 (1949). (92) Hunt, M., Weinmayr, V., and Sartori, M. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,467, 130 (April 12, 1949). (93) Ibid., 2,467,131 (April 12, 1949). (94) Ibid., 2,467,132 (April 12, 1949). (95) Hurd, C. D., U. S. Dept. Commerce, OTS Rept., PB 6814 (Nov. 1, 1944). (96) I. G. Farbenindustrie A.-G., Ibid., 17666, FIAT Microfilm Reel C69, Frames 24tb62. (97) Ibid., 44775, Enlargement Print of Frames 5769-71 of FIAT Microfilm Reel 146, PB 19920 (June 1944). (98) Ibid., 69052, Frames 808-14, Reel 162, PB 25606 (Dec. 12, 1939). (99) Ibid., 70062, FIAT Microfilm Reel G-22, Frames 22-26, 173-7, 194, 277-80, 283-93, 33843, 348-9, 358-63, 3704, 461-6, 482-3, 507-8, 511-12, 520-1, 5424, 557-8, 566-7, 675-7, 686-93,760-1,778-81,832-8 (1930-44). (100) Ibid., 70063, Reel G-23, Frames 247-50, 294-329, 385-7, 40212,442-6,540-1,577-8,582,584-7 (1932-46). (101) Ibid., 70188, Reel 0-37, Frames 5518-21, 5529-38, 5542-5, 554-64, 5893-6, 5995-6004, 6030-32, 6068-82, 6104-20, 6149-57, 6163-4, 6190-3, 6206.38, 6241-54, 6315-43, 6350-5 (194145). (102) Ibid., 70189, Reel 0-38, Frames 6417-8, 6423-7, 642842, 6470-90, 6446-50, 6677-84, 6690-7, 67024, 6707-19, 673444,6758-9,6770-1,6776-8,6866-70,6966-7,7019-23,7038-
44, 7103-4, 7117-20, 7123-37, 7179-84, 7190-1, 7194-5, 7200-7, 7214-18,7270-1,7305-6 (1937-1942). (103) Ibid., 70190, Reel 0-39, Frames 7829-30,7832, 7864 (1941-3). (104) Ibid., 70254, Reel A-31, Frames 7090-4, 7189-91, 7303-10, 73134,73756,7384-95 (1934-1941). (105) Ibid., 73616, Reel M-106, Frames 143947, 1450-8, 1471-3, 1479-85, 1492-1506, 1508-9 (1940-1946). (106) Ibid., 74197, BIOS Microfilm F. D. 235/47, S.O.1801/47, Part I, Frames 581, 583, 595, 599, 603, 606, 608, 622-3, 625, 634, 649-50, 677, 680, 714, 726, 764, 766, 769, 772-3, 777-80, 787,789,793, 795,801, 805,807,811,813,816,818,820,828, 831,833,836,839, 842, 845, 847, 851, 853,855,856,860,864, 866-7 (1931-1941). (107) Karrman, K. J., and Varpila, E., Svensk Kem. Tid., 60, 137-42 (1948). (108) Kharasch, M. S., and Zavist, A. F., J. Am. Chem. SOC.,70, 3526 (1948). (109) Kozlov, V. V., Doklady Akad. Nauk S.S.S.R.,61, 281-4 (1948). (110) Kozlov, V. V.,J. Gen. Chem. (U.S.S.R.), 18,242-50 (1948). (111) Ibid., pp. 891-5. (112) I W . , pp. 2094-102. (113) Koalov, V. V., and Kuznetsova, A. G., Ibid., 17, 2244-52 (1947). (114) Kratzl, K., Monatsh., 78, 173-4 (1948); oaterr. Akad. W k s . Wien, Math-naturw. K h s e , Sitrber. Abt., IIb, 157, 173-4 (1948). (115) Krstsl, K., (Isterr. Chem.-Ztg., 49, 143-9 (1948). (116) Krzikalla, U. S. Dept. Commerce, PB Rept. 633, Rept. 216 lAnril . 1942). ~. _=. .-1 -0 . , -. __, .
(117) Ibid., 663, Rept. 113 (April 9, 1943). (118) Kurakin, A. N., J . @en. Chem. (U.S.S.R.), 18,2089-91 (1948). (119) Lambert, A., and Rose, J. D., J. Chem. Soc., 1949,46-9. (120) Lambertz, U. S. Dept. Commerce, PB Rept. 73893, FIAT Microfilm Reel N-77, Frames 6257-60 (June 22, 1931). (121) Lecher, H. Z., and Adams, F. H. (to American Cyanamid Co.), U. S. Patent 2,483,213 (Sept. 27, 1949). (122) Lewis, A. H., and Ettling, A. C. (to California Research Corp.), I W . ,2,477,383 (July 2G. 1949).
1759
(123) Linetskaya, 2. G., and Sapozhnikova, N. V., J . Applied Chem. (U.S.S.R.), 21,876-80 (1948). (124) Lisk, G. F., IND.ENG.Cnmi., 40, 1671-83 (1948). (125) Ibid., 41, 1923-34 (1949). (126) Lafgren, N., Svensk Kem. Tid., 60,281-2 (1948). (127) Lukin, A. M., Dokladu Akad. Nauk S.S.S.R., 60, 591-4 (1948). (128) McNab, J. G., and Winning, C. (to Standard Oil Development Co.), U. 9.Patent 2,483,501 (Oct. 4, 1949). (129) Maeda, H., and Kobayashi, K., J . SOC.Chem. Ind. Japan, 45, 419-25 (1942). (130) Medersohn, U. S. Dept. Commerce, PB Rept. 73893, FIAT Microfilm Reel N-77, Frames 6674-9 (Feb. 28, 1931). (131) Meiser, W., Ibid., Frame 6402 (Dec. 8, 1934). (132) Meiser, W. (to General Aniline & Film Corp.), U. S. Patent 2,273,974 (Feb. 24, 1942). (133) Meiser, W., Morscbel, and Schuessler, U. S. Dept. Commerce, PB Rept. 73893, FIAT Microfilm Reel N-77, Frames 6520. 6523 (Dec. 1, 1938). (134) Mercier, J., Truv. SOC. phurm. Montpellier, 6, 64-5 (1946-7). (135) Mildner, U. 8. Dept. Commerce, P B Rept. 713, Rept. 288 (April 30, 1942). (136) Miller, A. L., Mosher, H. S., Gray, F. W., and Whitmore, F. C., J . Am. Chem. SOC.,71,3559-60 (1949). (137) Miron, S., and Richter, G. H., Ibid., 71,453-5 (1949). (138) Mitchell, J. E. (to Colgate-Palmolive-Peet Co.), U. S. Patent 2,480,592 (Aug. 30, 1949). (139) Morrell, S. H., Pickering, G. B., and Smith, J. C., J. Insl. Petroleum, 34, 677-91 (1948). (140) Moualim, R. J., and Peters, A. T., J.Chem. SOC.,1948, 1627-30. (141) Mueller, U. S. Dept. Commerce, PB Rept. 75336, Enlargement Print of Frames 2268-72 of FIAT Microfilm Reel C61,PB 17658 (February 1935). (142) Mueller, G. P., and Pelton, W. S., J . Am. Chem. SOC., 71, 1504-5 (1949). -. -. ,. (143) Naik, K. G., and Desai, C. M., J. Sci. Ind. Research (India), 7B, 193-5, 195-7 (1948). (144) Ott, K., and Schuessler, H., U. 8. Dept. Commerce, P B Rept. 73911, FIAT Microfilm Reel N87, Frames 4386-90 (April 4, 1930). (145) Pedersen, E. E., and Jensen, K. A., Acta Chem. Scand., 2, 651-6 (1948). (146) Peterson, W. D. (to General Aniline & Film Corp.), U. S. Patent 2,487,588 (Nov. 8, 1949). (147) Popkin, A. H. (to Sun Chemical Corp.), Ibid., 2,440,117 (April 20, 1948). (148) Proell, W. A. (to Standard Oil Co.), Ibid.. 2,489,316 (Nov. 29, 1949). (149) Ibid., 2,489,317 (Nov. 29, 1949). (150) Ibid., 2,489,318 (Nov. 29, 1949). (151) Pyridium Corp., Brit. Patent 602,882 (June 4,1948). (152) Regestad, 9.O., and Samuelson, O., Svensk Kern. Tid., 61, 8-10 (1940). .----, (153) Ruedrich, P. M. (to Griffin Chemical Co.), U. S. Patent 2,462,829 (Feb. 22, 1949). (154) Sallmann, R., and Graenacher, C. (to CIBA, Ltd.), Ibid., 2,479,782 (Aug. 23, 1949). (155) Salton, M. R. J., and Alexander, A. E., Research (London),2, 247-8 (1949). (156) Samuelson, O., and Westlin, A., Szisnslc. Papperstidn., 51, 17985 (1948). (157) Sandoz Ltd:, Swiss Patent 222,151 (Oct. 16, 1942). (158) Ibid., 222,152 (Oct. 16, 1942). (159) Ibid.,222,153 (Oct. 16, 1942). (160) Ibid., 222,154 (Oct. 16, 1942). (161) Ibid., 222,155 (Oct. 16,1942). (162) Ibid., 222,156 (Oct. 16, 1942). (163) Ibid.. 224,874 (Dec. 15, 1942). (164) Ibid., 224,875 (Dec. 15, 1942). (165) Ibid., 224,876 (Dec. 15, 1942). (166) Ibid., 224,877 (Dec. 15, 1942). (167) Ibid., 224,878 (Doc. 15, 1942). (168) Ibid., 224,879 (Dec. 15, 1942). (169) Ibid., 236,390 (June 16, 1945). (170) Ihid., 236,391 (dune 16, 1945). (171) Ihid., 238,268 (Oct. 16, 1945). (172) IMd., 238,269 (Oct. 16, 1945). (173) Ibid.,238,270 (Oct. 16, 1945). (174) Ibid., 238,272 (Oct. 16, 1945). (175) Scalers, M., and Foreter, W. S. ( t o American Cyanamid Co.), U. 8. Patent 2,455,096 (Nov. 30, 1948). (176) Schoeberl, A , , Wagner, A., and Rambacher, P., “FIAT Review of German Science 1939-1946, Preparative Organic Chemistry,” Part I, Karl Ziegler, senior author, pp. 363-8, Wieabaden, Office of Military Government for Germany Field Information Agencies Technical (British, French, arid U. S. A.), 1948.
.
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
1760
(177) Schowalter and Lien%acher, U. S. Dept. Commerce, OTS Rept., PB 70345, FIAT Microfilm Reel C16, Frames 1856266 (Feb. 17, 1942). (178) Schwartz, A. M., and Perry, J. W., “Surface Active Agents,
Their Chemistry and Technology,” New York and London, Interscience Publishers. 1949. (179) Severoceske Tukove Zavody (Drive Jiri Schicht) Rarodri Podnik, Brit. Patent 621,765 (April 19, 1949). (180) Shilov, E. A., and Kurakin, A. N., J . G a . Chem. (U.S.S.R.),
18, 2092-3 (1948). (181) Shuck, G. R., and Lingafelter, E. C., J. Am. C h a . Soc., 71, 1325-7 (1949). (182) Sigwart, U. S. Dept. Commerce, PB Rept. 73911, FIAT Microfilm Reel N87, Frames 4610-12 (May 10, 1932). (183) Simon, Ibid., PB Rept. 657, Rept. 240 (March 31, 1942). (184) Sisley, J. P., “Index of Sulfonated Oils and Modern Detergents,” Paris, Teintex, 1949.
Slinger. F. H.. Tatum. W. W.. and Imperial Chemical Industries, Ltd., Brit. Patent 619,034 (March 2, 1949). Smith, R. L., Crowley, D. J., and Waldo, P. G. (to SoconyVacuum Oil Co., Inc.), U. S.Patent 2,463,497 (March 1 , 1949).
Smyth, G. M. (to American Cyanamid Co.), Ibid., 2,454,679 (Nov. 23, 1948).
Spaeth, U. S. Dept. Commerce, 02“s Rept. , PB 70345, FIAT Microfilm Reel ‘216, Frames 18494-52 (Feb. 15, 1943). Spryskov,A. A.,J. Gen. Chem. (U.S.S.R.), 17, 591-600 (1947). Ihid., Ihzd., Ihid., Ibid.,
18, 98-102 (1948).
pp. 749-52. PP. 941-7.
pp.1370-5.
Staudinger, H., el al., “FIAT Review of German Science 19391946, Preparative Organic Chemistry,” Part 111, Karl Ziegler, senior author, pp. 67-76, Wiesbaden, Office of Military Government for Germany Field Information Agencies Technical (British, French and U. S. A,), 1948. Tatum, W. W., and Imperial Chemical Industries, Ltd., Brit. Patent 621,713 (April 14, 1949).
Vol. 42, No. 9
(196) Teuffert, U. S. Dept. Commerce, OTS Rept., PB 725, Rept. 179 (April 30, 1943). (197) Tietze, Ibid., 14998, FIAT Microfilm Reel C28, Frames 301-13 (April 9, 1937). (198) Timell, T., Svensk Papperstidn., 51, 254-8 (1948). (199) Truce, W. E., and Suter, C. &I., J. Am. Chem. Sac., 70, 3851-2 (1948). (200) Tsukervanik, I. P., and Poletaev, A. V., J . Gen. Chem. (U.S.S. R.), 17, 2240-3 (1948). (201) Ufimtsev, V. N., J . Applied Chem. (U.S.S.R.), 20, 1199-208 (1947).
(202) (203) (204) (205) (206)
Ibid:,-;283-5 (1947). Ihid., 1286-7 (1947).
Ufimtsev, V. N., J. Gen. Chem. (U.S.S.R.), 18, 1395-8 (1948). Wacek, A. V., and Kratzl, K., J . Pdgmer Sci., 3, 539-48 (1948). Weinmayr, V. (to E. I. du Pont de Nemours & Co.), U. S.Patent 2,467,170 (April 12, 1949). (207) Weissenborn, U. S. Dept. Commerce, UT$ Rept., PB 70428, FIAT Microfilm Reel E25, Frames 8 1 4 3 4 (May 11, 1944). (208) Wendland, R. T., and Smith, C. H., Proc. North Dakota Acad. Sei., 2, 40-3 (1949). (209) Wendland, R. T., Smith, C. E., and Muraca, R., J. Am. Chem. SOC., 71, 1593-5 (1949). (210) Wieland, T., Fischer, E., and Moewus, F., Ann., 561, 47-52 (1948). (211) Winkelmueller, U. S. Dept. Commerce, PB Rept. 74914, FIAT Microfilm Reel T31, Frames 4488-90,4511-714 (1936-37). (212) Wintringham, A. C., Moffatt, L. R., and Carland, R. (to American Cyanamid Co.), U. 9. Patent 2,479,990 (Aug. 23, 1949). (213) Witte, M. (to Allied Chemical & Dye Corp.), Ibid., 2,465,951 (March 29, 1949). (214) Witte, M., and Welge, M., Ibid., 2,465,952 (March 29, 1949). (215) Yakubovich, A. Y., andzinov’ev, Y. M., J. Gen. Chem. (U.S. S.R.), 17, 2 0 2 8 4 7 (1947). (216) Yoder, L., and Thomas, B. H., T m . ENG.CHEM.,41, 2286-9 (1949). (217) Yoder, L., and Thomas, B. H., J . Bid. Chem., 178, 363-72 (1949). RECEIVED June 16, 1050
Other Unit Processes HAROLD J. GARBER UNIVERSITY
OF TENNESSEE, K N O X V I L L E , TENN.
T
HE summary presented in this review section deals with advances made in calcination, condensation, desulfurization, and reduction, as represented by the literature published on these topics during the past several years. Inasmuch as the literature dealing with reactions activated by electrical discharges for this period is not sufficiently extensive for inclusion here, reporting on the progress in this field is deferred. Following the pattern established in the previous review, the literature cited is limited to papers that disclose significant information. Papers that merely elucidate minor phases of the four processes discussed are not included in this report.
CALCINATION The literature for the review period discloses relatively few innovations in techniques in this field or in the operation of shaft or rotary kilns. Numerous details concerning some of the newer types of lime kilns and their points of departure from the older types were discussed by Block ( 6 A ) . A paper by Lacy (27.4) also dealt with modern vertical lime kilns, and included a tabulation of the functions of the operating zones, the use of producer gas as a heat source, and the factors that determine the production capacity and thermal requirements. The influence of the method of charging, particularly of undersize feed, on such operating features as production rate, slagging of the refractory, and failure of fans was discussed by Azbe ( S A ) . In connection with the burning of dolomite in shaft-type kilns, Brumbaugh
( 7 A ) discussed rational methods for kiln design, selection of linings, thermal and material balances, and results of studies of movement of the charge during burning. Khodorov (22.4) reported data for experimental runs made on some automatically operated small shaft furnaces, emphasizing the advantages of low initial investment and operating charges for such units. Formulas, curves, and means for estimating the capacity of rotary kilns were discussed by Gibbs (IbA) and Atherton ( 1 A ) . Means of increasing the capacity of rotary kilns were proposed b y Khodorov (23A, 2 J A ) who made recommendations concerning such items as ratio of kiln diameter to length, pitch, temperature gradients, and length of sintering zone to obtain maximum capacity. Results of experiments using an oxygen-enriched air blast in the operation of a kerosene-fired kiln to secure higher cement production capacity, among other benefits, were disclosed by Lur’e and Val’berg (MA, 34A). The thermodynamics of lime manufacture was discusaed by Gibbs (14A, 1 5 A ) , who indicated where energy dissipation occurs and presented means to approach perfect kiln operation. Ways to increase the thermal efficiency of rotary cement kilns, primarily by heat recuperation, lengthening the burning zone, reducing the moisture content of the feed, and addition of small amounts of sodium carbonate to the feed were considered by Jaspers ( I 7 A 19A). The influence of recuperator chains, gas velocity, average gas and stock temperature, and final moisture content of the product on the experimentally determined heat transfer coeffi-
