PRODUCT AND PROCESS DEVELOPMENT from N,N‘-dibutyldiphenyl chlorohydrin.
ether-4,4‘-disulfonamide and epi-
Summary and conclusions
Like the bisphenols, primary aromatic sulfonamides such as p-toluenesulfonamide react with epichlorohydrin in alkaline solution a t moderate temperatures to form epoxide-containing products. However, unlike the reaction products of bisphenols with epichlorohydrin, these products cannot be gelled by amine or anhydride catalysts and will condense further to products of no epoxide content unless the reaction conditions are carefully controlled. The epoxide-containing products can also be formed by employing a very large excess of epichlorohydrin. Like phenols, secondary aromatic sulfonamides react with epichlorohydrin in alkaline solution to form epoxide-containing products. These can react further with excess sulfonamide to form hydroxyl-containing derivatives. Depending on their structure, certain disecondary sulfonamides react with epichlorohydrin t o form one of two productseither high melting products of low epoxide content or products of appreciable epoxide content. Like the bisphenol-based resins, the latter materials can be gelled by amine or anhydride catalysts. The tendency of the disecondary sulfonamides to form one or the other of these products can be correlated with their ease of ring formation. This cyclization hypothesis can be extended as one possible explanation of the reaction products observed with p-toluenesulfonamide and epichlorohydrin. Certain sulfonamides give no water-insoluble products with epichlorohydrin in alkaline solution. Acknowledgment
The author wished to thank J. R. Ladd, General Electric Co. Research Laboratory, for furnishing samples of some of the sulfonamides used in this investigation. Literature cited (1) Amundsen, L. H., and Longley, R. I., Jr., J . Am. Chem. SOC.,62, 2811 (1940).
(2) Boyd, D. R., and Marle, E. R., J. Chem. SOC.,93, 838 (1908). (3) Bradley, T. F. (to Shell Development Co.), U. S. Patent 2,541,027 (May 11, 1948). (4) Costan, P., Ibid.,2,324,483(July 20,1944). (5) De Trey Frhres 8. A., Brit. Patent 518,057 (Feb. 15, 1940). (6) Ibid.. 579,698 (Aug. 13, 1946). (7) Fairbourne, A., Gibson, G. P., and Stephens, D. W., J. Chem. Soc., 1932,p. 1965. (8) Field, J. E., Cole, J. O., and Woodward, D. E., J . Chem. Phya., 18, 1298 (1950). (9) Field, L.,and Grunwald, F. A., J. Am. Chem. Soc., 75, 938 (1954). (10) Greenlee, S. 0. (to Devoe and Raynolds Go.), U. S. Patent 2,582,985 (Jan. 22, 1952). (11) Howard, C. C.. and Marckwald, W., Ber., 32, 2036 (1899). (12) Jones, G. D., J. Org. Chem., 9,484 (1944). (13) Ladd, J. R., General Electric Co. Research Lab., private com-
munication. (14) Marckwald, W., and Fehr. van Droste-Huelshoff, A., Bsr., 31, 3261 (1898). (15) Marle, E. R., J . Chem. SBC,,101,305 (1912). (16) Miller, H. (to Dyanamit A.-G. vorm. Alfred Nobel and Co.), Ger. Patent 810,814 (Aug. 13, 1951). (17) Moss, W. H., Brit. Patent 483,087 (April 12, 1938). (18) Ogg, C. L., Porter, W. L., and Willits, C. O., IND. ENG.CHEM., ANAL.ED., 17,394 (1945). (19) Ohle, H., and Haeseler, G., Ber., 69B, 2324 (1936). (20) Siggia, Sidney, “Quantitative Analysis Via Functional Groups,” p. 4, Wiley, New York, 1949. (21) Simons, J. K. (to Allied Chemical and Dye Gorp.), U. S. Patent 2,671,771 (March 9, 1954). (22) Simons, J. K. (to Libbey-Owens-Ford Glass Co.), Ibid., 2,643,244 (June 23, 1953). (23) Suter, C.M., J . Am. Chem. SOC.,53, 1112 (1931). (24) Truchot, P., Ann., 138, 297 (1866.). (25) Ibid., 140, 244 (1866). (26) Werner, E. G. G., and Farenhorst, E., Rec. trav. chim.,67, 438 (1948). (27) Werner, E. G. G., and Farenhorst, E. (to Shell Development Co.), U. S. Patent 2,467,171 (April 12, 1949). (28) Yanbikov, Ya. M., and Dem’yanov, N. Ya., J. Gen. Chem. (U.S.S.R.), 8, 1545 (1938). R E C E I Y ~for D review September 17, 1954.
ACCEPTED July 5, 195s.
Uncatalyzed Coal Hydrogenolysis M. G. PELIPETZ, J. R. SALMON, J. BAYER, AND E. L. CLARK’ Coal-fo-Oil Research, U. S. Bureau of Mines, Brucefon, Pa.
H
”
YDROGENOLYSIS of Rock Springs coal at 400” C. in the presence of tin and molybdenum and under initial hydrogen pressures of 500 to 4000 lb. per sq. inch gage has been studied, and the results have been reported (9). In that study the rate of transformation of benzene-insoluble matter of coal to benzene solubles, water, and gaseous product was used for quantitative evaluation of catalyst activity and for estimation of the extent of hydrogenolysis as a function of initial hydrogen pressure. For a better underst.anding of the function of the catalyst, a similar study has now been made of the uncatalyzed hydrogenolysis of Rock Springs coal. Material used was bituminous C Rock Springs coal
Bituminous C coal from the Rock Springs bed, Superior, Wyo., was used. It was air-dried and pulverieed to pass through a 200-mesh screen. I t s ultimate composition was as follows: 1
Present address, Israel Mining Co., Haifa, Israel.
October 1955
% Hydrogen Carbon Nitrogen
Sulfur Ox gen AS{
Moisture
4.54 71.50 1.48 1.20 11.88 5.40 2.00
The experimental procedure and method of evaluation of the results were similar to those described previously ( 3 , 4 ) . Conversion of benzene-insoluble matter of coal to benzene solubles, water, and gas i s a first-order reaction
Operational conditions, product distribution, and hydrogen consumption are summarized in Table I. As in the case of catalytic hydrogenolysis of coal, asphaltene is the main product of uncatalyzed hydrogenolysis at 400’ C. The time of reaction reported in Table I includes 8 5-minute correction factor for the preheating and cooling periods. Figure 1 shows the logarithms of the percentage of remaining benzene insolubles as functions of contact time. Extensive experience with Rock Springs coal has
INDUSTRIAL AND ENGINEERING CHEMISTRY
2101
PRODUCT AND PROCESS DEVELOPMENT Table I.
Product Distribution from Uncatalyzed Hydrogenolysis of Coal at
Initial Hydrogen Reaction Pressure Time Lb./Sq. Inch b s g e hlin.'
Experiment
No.
2056 2054 2052 2047 2040 2048 2055
500 500 500 1000 1000 1000 2000 2000 2000 3000 3000
2039 2041 2037
35 65 185 35 65 185 35 65 185 65 185
,
400" C.
Grams/100 Grams M.A.F. Coal
Benzene Bolubles
phaltene
Oil
Benzene solubles
89.16 84.61 74.79 86.47 82.87 57.77 79.07
0.53 2.76 7.02 3.00 2.56 22.25 4.61
1.10 1.66 2.87 0.88 2.66 3.53 3.75
1.63 4.42 9.89 3.88 5.21 25.78 8.30
46.40 59.51 23.09
30.46 22.65 50.90
4.19 3.86 8.06
34.65 26.51 58.96
in-
AS-
shown that it contains 3% organic matter resistant to hydrogenation and that, consequently, may be regarded as an impurity.
Gaseous hydrocarbons
Carbon dioxide
Water
Hydrogen consumed
3.98 4.94 6.47 3.75 4.99 7.09 4.79
2.47 2.96 3.60 2.87 3.13 3.86 3.99
2.87 3.38 6.27 3.38 4.33 6.97 4.72
0.54 0.45 1.00 0.77 1.30 2.15 1.32
10.00
3.40 3.86 3.22
2.76 5.54 8.32
3.20 2.20 3.93
6.16
9.32
A corresponding correction, therefore, has been made in constructing Figure 1 that indicates that the conversion of benzeneinsoluble matter of coal to benzene solubles, water, and gas was a first-order reaction with respect to benzene insolubles remaining. The specific reaction rate constants, K , determined from Figure 1, are given in Table I1 and are plotted as functions of initial hydrogen pressure in Figure 2. The units of K are min.-', and those of P are Ib. per sq. inch gage. For comparison, specific reaction rate constants for the hydrogenolysis of Rock Springs coal in the presence of tin and molybdenum are included (1). The plots of Figure 2 illustrate the rectilinear dependence between K and initial hydrogen pressure, P , which is K = 3 X 10-P for the uncatalyzed reaction as compared with K = 1.5 X lO-sP 0.0225 for hydrogenolysis in the presence of molybdenum. These relationships permit a direct comparison of catalytic activities. For example, at 400' C. the rate of disappearance of benzene insolubles in the presence of 1% molybdenum under an initial hydrogen pressure of 500 lb. per sq. inch gage is equal to the rate of conversion in the presence of 1% tin at an initial hydrogen pressure of 2000 lb. per sq. inch gage. In the absence of catalyst, an equal reaction rate is obtained only when the pressure is 10,000 lb. per sq. inch gage.
+
v, 0
Figure 1. Organic benzene insolubles remaining during uncatalyzed hydrogenation of Rock Springs coal at 400" C.
Coal acts as homogeneous material during hydrogenation
Figure 3 represents a plot of benzene solubles as a function of remaining benzene insolubles. The linear relationship of these two quantities indicates that coal behaves as a homogeneous substance during hydrogenation. For comparison. similar plots for hydrogenation in the presence of molybdenum and tin are produced. These curves indicate the effect of a catalyst on the
0072 0~4-
Uncatolyzed
A Tin 0 Molybdenum
E
-
056
c z -
z x- 048-
+-
I
6 0400 Y
5z
032-
0
"
9 LL u Y
g
024-
016
1
-
-
VI
Y Y
: IO m I N I T I A L HYDROGEN PRESSURE. P S I
G
Figure 2. Effect of pressure on specific reaction rate constants for uncatalyzed hydrogenation of Rock Springs coal at
400" C. 2102
0
10
20
30 40 SO 60 70 SO SO INSOLUBLES REMAINING, W E I G H T - P E R C E N T M A F COAL
BENZENE
100
Figure 3. Relationship of benzene insolubles remaining to benzene solubles produced asphalt) (oil
+
INDUSTRIAL A N D ENGINEERING CHEMISTRY
Vol. 47, No. 10
PRODUCT AND PROCESS DEVELOPMENT production of benzene solubles. In the presence of a catalyst, a unit of coal produces more benzene-soluble material than in its absence. In a preceding paper (3)the formation of benzene solubles as a function of benzene insolubles remaining for hydrogenation in the presence of tin and molybdenum was plotted on a single curve. This system was used because the experimental
Table II. Specific Reaction Rates, K, for Hydrogenolysis of Rock Springs Coal at 400' C. Initial Hydrogen Pressure Lb./Sq. Inch G'age
K.
Minutes-' Uncatalyzed
500 1000 2000 3000
0.0015 0.0030 0.0060 0.0090
Molybdenum
0 Molybdenum
500 1000 2000 3000 4000
0,030 0.0375 0,0525 0.0675 0,0825
Tin 0.015 0.030 0.045
1000 2000 3000 0
10
Figure 4.
20 30 40 50 60 10 80 B E N Z E N E I N S O L U B L E S REMAINING, WEIGHT-PERCENT M A ? . C O A L
90
100
Relationship of hydrocarbon gas production to conversion of benzene insolubles
data for each catalyst were concentrated in two different areas and it was difficult to determine the real direction of the separate curves. After careful examination of the distribution of the experimental points on a plot made on a large scale, it was decided that two separate curves better illustrate these two hydrogenations. Table I shows that gaseous hydrocarbons represent a sizable portion of the products obtained from coal hydrogenation. Formation of gaseous hydrocarbons as a function of remaining benzene insolubles is plotted in Figure 4 for uncatalyzed as well as for catalyzed hydrogenation. These curves show that, for the same amount of conversion, uncatalyzed hydrogenation resulted in the highest production of gaseous hydrocarbons, and hydrogenation in the presence of molybdenum resulted in the lowest amounts. The increased amounts of gaseous hydrocarbons, formed in the absence of catalyst, probably resulted because of the longer times during which coal and its products of hydrogenation
I
.... MolybdenYm
-4
z*
zi 0
Figure
10 20 30 40 50 60 70 80 BENZENE lNSOLUBLES REMAINING, WEIGHT-PERCENT M A F COAL
5.
90
100
Relationship of carbon dioxide production to conversion of benzene insolubles
were a t reaction temperature. For exampIe, comparison of specific reaction rates indicates that, to obtain the same conversion at 500 lb. per sq. inch gage initial pressure, the contact time in the presence of molybdenum is only 1/20 that required in the absence of catalyst. A comparison of the quantities of gaseous hydrocarbons formed under 500 and 3000 lb. per sq. inch gage initial hydrogen pressure indicates that a t the same degree of coal conversion more gaseous hydrocarbons were formed a t the lower hydrogen pressure. This observation is in agreement with information from the operation of commercial hydrogenation plants ( 4 ) . Formation of carbon dioxide as a function of remaining benzene insolubles is presented in Figure 5 that indicates that
October 1955
2
I
i
l
there is no change with time in yield of carbon dioxide when coal is hydrogenated in the absence of catalyst. On the other hand, the yield of carbon dioxide decreases with time in the presence of catalyst, especially with an active catalyst such as molybdenum. Because an exact determination of water is very difficult in batch autoclave experiments, the data on the formation of water are more scattered than the rest. In spite of this fact, Figure 6 shows that more water is formed as hydrogenation progresses. More water is produced in the later stages of hydrogenation in the presence of molybdenum. This increase is due to the hydro'genation of carbon dioxide to methane and water, and to the activity of molybdenum in the elimination of oxygen. This comparison of data obtained on uncatalyzed hydrogenation of coal with its hydrogenation in the presence of active catalysts indicates that, in addition to increasing the rate of the reaction, catalysts also direct the reaction to the production of more valuable liquid products. Literature cited Donath, E. E.,private communication, 1953. Pelipeta, M. G., Salmon, J. R., Bayer, J., and Clark, E. L.,IND. ENG.CHEM.,45, 806 (1953). (3) Pelipetz, M. G.,Weller, S., and Clark, E. L., Fuel, 29, 208-211 (1950). (4) Weller, S., Pelipeta, M. G., Friedman, S., and Storch, H. H., IND.ENG.C H E M .42, , 330-334 (1950). RECEIVED for review January 18, 1955. ACCEPTED April 6, 1955. Presented before the Division of Gas and Fuel, ACS, May 1953.
INDUSTRIAL AND ENGINEERING CHEMISTRY
2103
