364
Ind. Eng. Chem. Prod. Res. Dev., Vol. 18, No. 4, 1979
Table I. Falex-Load Carrying Capacitya base oil, % wt
chlorinated chlorine jojoba, content, % wt % wt
100 90 75 50 90 75 50 90 75 50
0 10 25 50 10 25 50 10 25 50
Mechanical Properties. Chlorinated jojoba oil, with varying percentages of chlorine, was tested for load carrying capacity at Frankford Arsenal, Philadelphia. Some typical results are given in Table I. The halogenated derivative improved moderately the load carrying capacity of the base oil, for chlorine contents between 11 and 15% weight. A substantial increase was observed when the percentage of chlorine went up to 21 9% (saturation of the double bonds).
load carrying capacity, lb
0 11 11 11 15 15 15 21 21 21
800
1000 1000 1000 1000 1000 1000 3000 3500 3700
Acknowledgment Mr. J. Messina, Frankford Arsenal, Philadelphia, Pa., performed the load-carrying tests. Partly financed by Negev Jojoba Co.
A.S.T.M. Method D-2670.67 (1972).
methylene bromide, shortening the overall analysis time. Trial runs with jojoba oil effectively indicated that titration with potassium iodide/sodium thiosulfate within 1min of addition yielded an excellent estimate of the iodine value. Influence of Inhibitors. Addition of a radical inhibitor like hydroquinone produced a drastic decrease in the rate of reaction, particularly with high dielectric constant solvents. This meant that a radical mechanism was operating in parallel to the molecular path given in eq 10. We can quote here the overall scheme (eq 11)given by Sergeev et al. (1973). Br
I
*
-CH-CH=C
radical path
I C
+ Br2
I
-
-CHBr-CH=CHBr
,c-c-
'
*'
I malecular
I I
Erg path (C=C)(Br2)2
\
palh polar
1
\
I
-
I
I
-C-Br
/ -7-
I
Literature Cited American Oil Chemists' Society, "Official and Tentative Methods", 2nd ed., Chicago. Ill.. 1964. A.S.T.M.,"Bod( of Standards, American Society for Testing Materials", Philadelphia, Pa., 1973. Barmford, C. H., Tipper, C. F. H., "Comprehensive Chemical Kinetics", Voi. 9, Eisevier, London, 1973. Bodrikov, I . V., SpirMonova, S. V., Smolyan, 2. S., Subbotln, A. I., Zh. Org. Khim., 6, 684 (1975). Clegg, G. T., Winter, P., J. Am. Oil Chem. Soc., 48, 433 (1972). De La Mare, P. E. D., J. Chem. SOC.,3, 3823 (1960). De La Mare, P. B. D., Boiton, R., "Electrophilic Addition to Unsaturated Systems", Eisevier, Amsterdam, 1966. Kochi, J. K., "Free Radicals", Vol. 11, Chapter 15, Wlley, New Ywk, N.Y., 1972. Lyness, W. I.,Quackenbush, F. W., J. Am. OilChem. SOC.,32, 521 (1955). Menting, J. E., Grimm, R. A,, Stirton, A. J., Weil, J. K., J. Am. OilChem. Soc., 45, 895 (1966). National Academy of Sciences, Committee on Jojoba Production Systems Potential, "Jojoba Cultivation Feasibility for Indian Lands", Washington, D.C., 1977. Poutsma, M. L., J. Am. Chem. Soc., 87, 2161 (1965). Sergeev, 0. V., Serguchev, Y. A., S m h v , V. V., Usp. Khim., 42, 1545 (1973). Serguchev, Y. A., Konyushenko, V. P., Zh. Org. Khim., 11(3), 46 (1975). Serguchev, Y. A., Sergeev. G. B., Ukr. Khim. Zh., 38, 4 (1972). Sonntag, N. 0.V., J. Am. Oil Chem. Soc., 40, 199 (1963). Teeter, H. M., Jackson, J. E.,J. Am. Oil Chem. Soc., 26, 535 (1949). Van Atta, G. R., Houston, D. F., Dietrich, W. C., J. Am. 0ilChem. SOC.,24, 209 (1947). White, E. P., Robertson, P. W., J. Chem. Soc., 1509 (1939). Wisniak, J., Progr. Chem. Fats Other Lipus, 15, 167 (1977). Wisniak, J., Benajahu, H., Id.Eng. Chem. Rod. Res. Dev., 14, 247 (1975). Wisniak, J., Benajahu, H., I d . Eng. ch8m. Prod. Res. Dev., 17, 335 (1978).
Received f o r review May 18, 1979 Accepted August 2, 1979
Gellants for Control of Petroleum Spills on Water S. K. Bahloul, Alfred A. Donatelll,' Wllllam W. Bannlster, and John W. Walkinshaw Chemical Engineering and Chemistty Departments, University of Lowell, Lowell, Massachusetts 0 1854
Gelation is a promising method for the control and cleanup of hydrocarbon liquid spills on water. The hydrocarbon is converted into a gel when a solution consisting of 70 % Amine D, 15 % ethyl alcohol, and 15 % benzyl alcohol by volume is added to the liquid and subsequently reacted with carbon dioxide. Spills on water were simulated with substances such as no. 2 fuel oil, Avgas 145, pentane, isooctane, and cyclohexane, and for each case the organic phase was converted successfully into a gel. Gel strength increased with decreasing gelation temperature and also was affected slightly by salt water.
Introduction Since the transportation of liquid chemicals on waterways is an integral part of our industrialized society, the potential for an accidental discharge or spill of chemicals
on water always will exist. Legislation can be used to provide strict transportation and handling regulations to minimize the chances of an accident, but the human factor cannot be controlled completely to eliminate the possibility
0019-7890/79/1218-0364$01.00/00 1979 American Chemical Society
Ind. Eng. Chem. Prod. Res. Dev., Vol. 18, No. 4, 1979 365
of a spillage. Because chemical spills have far-reaching ecological and social implications, we must be well prepared to handle an accident. The various aspects for confronting and combatting such a problem consist of methods of prevention, control and containment, and cleanup. Methods of prevention are usually met by regulations regarding the handling of chemicals and by proper training of personnel involved in the transportation. Methods of control, containment, and cleanup depend upon the type of spill, its size, and location. Publications by the U S . Department of the Interior (1969), Hoult (1969), the American Petroleum Institute and Federal Water Pollution and Control Administration (1970), the Environmental Protection Agency (1970,1972), and Johnson and Bowen (1974) cover some of the latest methods for confronting and combatting chemical spills. This investigation is concerned with only a specific type of cleanup method, the gelation of a small hydrocarbon liquid spill on water. The concept of gelling or thickening hydrocarbon liquids has been known for a long time. During World War 11, gasoline was thickened in order to obtain a satisfactory fill for flame throwers (Kirk-Othmer, 1964). This eventually led to the development of napalm, in which naphthenic and palmitic acids as major constituents were found to be a satisfactory thickener of gasoline. More recently, a patent was issued to Bannister et al. (1972) which dealt with gelling hydrocarbon liquids by reacting primary or secondary amines with carbon dioxide. The reaction of long chain aliphatic amines with carbon dioxide forms carbamate salts which physically entrap the hydrocarbon liquid. The carbamate salts have sufficient hydrophobic properties to permit gelation of the liquid even in the presence of water. In previous work, Bannister (1976) concluded that the best gelling agent solution consisted of 70% Amine D, 15% ethyl alcohol, and 15% benzyl alcohol. The Amine D is a trade name for a mixture of related primary amines with dehydroabietylamine as the dominant component, and it is manufactured by Hercules, Inc. In this paper, we will show that gelation can be used to combat hydrocarbon liquid spills on fresh and salt water. The efficiency of the gelation process was evaluated by measuring the strength of the gelled materials that were made with different amounts of gelling agent solution and at various water temperatures. A gelometer also was designed and constructured in order to measure the strength of the gelled hydrocarbons. Experimental Section Development of a Gelometer. Gel strength is usually measured on a Bloom gelometer (Bloom, 1925). Since this instrument was not readily available, a gelometer was designed and built. Figure l a is a diagram of our gelometer, and Figure l b illustrates the concepts of the device. A small metal ball of diameter D is attached to an electromagnet located at a fixed distance h above the gel surface. When the electromagnet is de-energized, the ball is released and falls freely to the gel surface. The kinetic energy of the ball upon impact will cause it to penetrate a distance P into the gel. The gel strength is determined by measuring the exposed portion of the ball R. As gel1 strength increases, the exposed portion of the ball also will increase. For testing the gels made in this work, the electromagnet was located at a distance of 10 cm above the gel surface, and the metal ball, which weighed 4.7 g, had a diameter of 1.27 cm. Gelation of Hydrocarbon Liquids. The following five hydrocarbons were used for simulating spills on water: no. 2 fuel oil, Avgas 145, pentane, isooctane, and cyclohexane.
(b) Figure 1. (a) Gelometer used for measuring gel strength: A, electromagnet; B, metal ball; C, gel sample; D, adjustable platform. (b) Gelometer variables that are dependent upon gel strength.
The no. 2 fuel oil and Avgas 145 were selected because of large commercial usage. Pentane, isooctane, and cyclohexane were chosen to represent a straight chain, a branched, and a cyclic hydrocarbon, respectively. The simulation and subsequent gelation were performed according to the following procedure yielding samples with a thickness of 1.2-1.3 cm: (1)Fifty milliliters of either fresh or salt water was placed in a 100-mL beaker. (2) Twenty milliliters of the hydrocarbon liquid was added to the beaker. (3) The appropriate amount of gelling agent solution was added to the beaker. This amount was based on a volumetric ratio X, which was equal to the volume of gelling agent solution per unit volume of hydrocarbon liquid. (4) Some turbulence was introduced into the system by slightly shaking or stirring the liquid mixture. (5) A small amount of dry ice was sprinkled uniformly over the liquid mixture, and a short period of time was allowed for gel formation. (6) The gel then was removed from the beaker and tested for strength. To simulate several water temperatures, the temperature of the mixture was varied in the following manner. For temperatures above ambient, the glass beaker was placed in an electrically heated water bath. On the other hand, temperatures below ambient were obtained by surrounding the beaker with crushed dry ice. The temperatures were held constant at the desired value until the gel was formed and removed for strength testing. Since the elapsed time between sample removal and testing was very short, it was assumed that temperature changes within the sample were negligible during this period. Results and Discussion Figure 2 shows the effect of gelling agent concentration on the strength of the hydrocarbon gels made in fresh water at 298 K. Generally, strength increased rapidly at lower concentrations and approached an upper limit at higher concentrations. When results for the different liquids are compared, it is apparent that the gel strengths are significantly different at the lower concentrations. However, at higher concentrations, the strengths tend to
368 Ind. Eng. Chern. Prod. Res. Dev., Vol. 18, No. 4, 1979 12-
12-
10-
10-
08
3806
z
-
V
04
04-
I
I
02 c
Oh
06
a'
0.k
o.$
02
0;s
0.k
f i -
-
d"
-
' 0
0.05
:j
0.8
Table I. Optimum Amount of Gelling Agent Solution for the Gelation of the Hydrocarbon Liquids hydrocarbon liquid
type of water
Avgas 145 cyclohexane no. 2 fuel oil
fresh fresh fresh salt fresh salt fresh salt
pentane
o.2
Ol'O
0.20
Figure 4. Comparison of the strengths of no. 2 fuel oil gels made in fresh water at temperatures of 283 K, 0,298 K, 0, and 313 K, 0.
isooctane
0.k
015
X
X
Figure 2. Comparison of the strengths of the hydrocarbon gels made in fresh water at 298 K: 0,cyclohexane; 0 , Avgas 145; 0, isooctane; D, no. 2 fuel oil; 0, pentane.
t
010
Ol5
O.:O
X
Figure 3. Comparison of the strengths of no. 2 fuel oil gels made in fresh water, 0,and salt water, 0 , at 298 K.
approach the same maximum value. Pentane is the only exception to this behavior. For reasons which currently are unclear, pentane only formed weak gels. The effect of salt water on the gelation of no. 2 fuel oil is shown in Figure 3. A t lower concentrations of gelling agent, the gelation process was less effective in salt water than in fresh water. In order to obtain a strength equal to that in fresh water, more gelling agent was required. Since gelation probably occurs by hydrogen bonding among the molecules within the system, the presence of salt in the water hinders the bonding process, so more gelling agent was required to overcome the interference. The other hydrocarbons showed a similar behavior although no. 2 fuel oil seemed to be affected more by the salt water environment. Figure 4 illustrates the effect of temperature on the gelation of no. 2 fuel oil. As the temperature was increased from 283 to 313 K, the gel strength decreased. This behavior is reasonable if the gel is considered to be similar to a liquid of very high viscosity. As the temperature of a liquid increases, its viscosity decreases which corresponds to a decrease in gel strength. The effect of temperature on gels of the other hydrocarbons, although not investigated, probably would be similar. Finally, Table I lists the optimum amount of gelling agent for the gelation of the liquids examined in this work. It is apparent that some of the liquids required less gelling
o p t amt of gelling agent, temp, K 298 29 8 283 298 31 3 298 29 8 298 298 298
X 0.10
0.10-0.12 0.12 0.12 0.20 0.16-0.18 0.12 0.12 0.18 0.18
agent to form strong gels. For example, gels of Avgas 145 and cyclohexane were formed more easily followed by gels of no. 2 fuel oil and isooctane. Pentane proved to be the most difficult liquid to convert into a gel. The above results show that the gelation concept can be used to recover hydrocarbon liquids from water. After a strong gel is made, it can be removed from the water surface by a skimming device. Then a method such as a centrifugal separation can be used to separate the harvested gel into its components. The hydrocarbon can be recovered, and the carbamate salt can be reconverted to the mother amine by treatment with either a strong base or by the application of heat so that it may be reused. Conclusions This investigation has shown that hydrocarbons which are immiscible with water can be converted into a gel. Five different liquid spills on water were simulated, and for each case the liquid could be gelled and removed from the water. The gelation process was affected only slightly by salt water, and gel strength was shown to decrease with increasing temperature. From a practical standpoint, gels of adequate strength and integrity were made, and it seems that this concept potentially could be used for the control and cleanup of small spills on inland waterways and oceans. At the present time, further work is being performed to improve the gelation process and to simulate environmental conditions more accurately. Literature Cited American Petroleum Institute and Federal Water Pollution and Control Administration, "Proceedings of the Joint Conference on hevention and Control of Oil Spills", 1970. Bannister, W. W., Pennance, J. R., Curby, W. A,, US. Patent 3684733 (1972). Bannister, W. W. "Gelation of Oil Slicks by Amine Carbamates as an Adjunct to U.S. Navy Oil Spill Recovery Operations", 1976.
-
Ind. Eng. Chem. Prod. Res. Dev., Vol. 18, No. 4, 1979 367 Bloom, 0. T., US. Patent 1540979 (1925). EnvironmentalProtection Agency, Office of Research and Development, "Oil Skimming Devices", May 1970. Envlronmental Protection Agency, Office of Water Programs, "Control of Oil and Other Hazardous Materials", Sept. 1972. HOUR, D. P. "Containment of Oil Spills by Physical and Air Barriers", MIT, Boston, 1969. Johnson, E., Bowen, S., "The Recovery and Processing of Hazardous Spills in Water", JBF Scientific Corp., 1974. Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd ed, Vol. 4, Wiley, New York, 1964.
U.S. Department of the Interior, Water Quality Lab., "Chemical Treatment of Oil Slicks", March 1969.
Received f o r review May 24, 1979 Accepted July 10, 1979
The authors wish to acknowledge the financial support provided by the Environmental Protection Agency for this work.
Instrumental Studies of Coal Liquefaction Takeshl Okutani, Shinichl Yokoyama, and Ryolchl Yoshlda The Government Industrial Development Laboratory, Hokkaido, 4 1-2 Hgashi-Tsukisamu, Toyohira-ku, Sapporo 06 1-0 1, Japan
Tadao Ishil Department of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060, Japan
Phenomenological studies of coal and catalyst in the course of h&pressure hydrogendysis of coal with r&mud-sulfur catalyst were carried out with a scanning electron microscope (SEM) and an electron probe X-ray microanalyzer (EPMA). The mechanism of catalytic action for coal hydrogenolysis was discussed. From the results of SEM observations, it was noted that the hydrogendysis of coal with catalyst proceeded from the adjacent catalyst particles. From the results of EPMA analysis, it was found that iron oxide in red-mud reacted with hydrogen sulfide, which was formed by reaction of sulfur added as the promoter with hydrogen, to iron sulfide in the course of coal hydrogenolysis. The S/Fe mole ratio of iron sulfide decreased with increasing reaction temperature over 400 OC. The mechanism of catalytic action of red-mud-sulfur catalyst was discussed on the basis of formation and decomposition of hydrogen sulfide.
Introduction Many catalysts are used in the hydrogenolysis of coal under high-pressure hydrogen. One of the catalysts used is red-mud, which is a waste in the Bayer process, to which sulfur is added as a promoter. Ishii et al. (1968, 1969) studied the red-mud-sulfur catalyst in high-pressure hydrogenolysis of coal using differential thermal analysis. They found that Fe203in red-mud changes to FeS in the course of coal hydrogenolysis, when the catalytic activity appears. On the other hand, the catalytic effects of iron sulfide present in coal on the hydrogenolysis of coal (Mukherjee and Chowdhury, 1976) and the Solvent Refined Coal Process (Wright and Severson, 1972) have been studied. In the present paper, the phenomenological studies of the high-pressure hydrogenolysis of Soya Koishi coal with red-mud-sulfur catalyst were carried out. A scanning electron microscope (SEM) and an electron probe X-ray microanalyzer (EPMA) were applied in this study. The mechanism of catalytic action for coal hydrogenolysis was discussed. Experimental Section Material. The results of proximate, low-temperature ash (LTA) and ultimate analysis on a d.m.f. (dry mineral free (Hasegawa et al., 1973)) basis of Soya Koishi coal are given in Table I. This coal is a low-rank bituminous coal with relatively high ash content and very low sulfur. The LTA is the content of mineral matter of coal measured by a low-temperature ashing technique by which the mineral
matter from coal can be obtained in a relatively unaltered state (Gluskoter, 1965). Table I1 presents the results of atomic absorption analysis of red-mud. Sulfur as a promoter and hydrogen were analytical grade commercial material and used without further purification. Sample Preparation. In order to observe samples by SEM and EPMA, pellet-like disks of sample coal were prepared and these pellets were hydrogenated under highpressure hydrogen. Coal powder (100 mesh sieve passed), red-mud, and sulfur (200 mesh sieve passed) were well mixed in the weight ratio 1oO:lO:l. The mixture of 200 mg was pressed into a pellet of 10 mm X 1.7 mm at 49 MPa in vacuo for 10 min. Apparatus. An autoclave of 115 mL was used as the reactor. A schematic diagram of the experimental reactor is presented in Figure 1. Four pellets were placed in the sample holder as shown in Figure 1 and inserted into the autoclave. Experimental Procedure. Initial hydrogen pressure of 7.8 MPa at room temperature, reaction temperatures up to 300, 350, 400, and 450 "C, and a heating rate of 2.5 "C/min were used. The reaction pressures were about 12.7, 13.5, 14.1, and 15.2 MPa at 300,350, 400, and 450 "C, respectively. After heating up to the prescribed temperatures, the autoclave was immediately cooled at a cooling rate of 2.5 "C/min down to room temperature. The oil and asphaltene produced were extracted from two pellets with benzene in a Soxhlet extractor. These extracted pellets were dried at 107 "C in vacuo. Conversions were estimated
0 1979 American Chemical Society
