US2010357A

US2010357A - Process of treating hydrocarbon oils and bituminous materials

Info

Publication number: US2010357A
Application number: US430200A
Authority: US
Inventors: Fisher Alfred
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 1930-02-21
Filing date: 1930-02-21
Publication date: 1935-08-06
Anticipated expiration: 1952-08-06

Description

A. FISHER 2,010,357

PROCESS OF TREATING HYDROCARBON OILS AND BITUMINOUS MATERIALS Aug. 6, 1935.

Filed Feb. 21, 1950 fzifenior. fllfred fisher, J27

ldztness Patented Aug. 6, 1935 UNITED STATES PATENT OFFICE PROCESS OF TREATING HYDROCARBON OILS AND BITUMINOUS MATERIALS Alfred Fisher, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, Ill., a corporation of South Dakota Application February 21, 1930, Serial No. 430,200

4 Claims.

' conversion of various mixtures of bituminous material such as various coals, lignites, peats, tars, pitches,- etc., with liquid hydrocarbons together with other substances in a dispersed or emulsified form at elevated temperatures with or without the use of catalysts so as to produce lower boiling point hydrocarbons and coke.

Among the objects of my invention is the utilization of low grade coals and coal wastes as well as the higher grade coals in the treatment of mixtures of oil and the bituminous materials for the production of a highly anti-knock motor fuel. Coal breeze and fines which are usually of the lowest economic value or constitute a waste are especially suitable for processing according to the method of my invention. This material being all ready resolved to a fine state of division does not require much further pulverization to treat by my process. These materials as well as lignites, tars, pitches, gilsonite, grahamite, Montan wax, shales and the like, or mixtures thereof, are treated to produce a coke and a maximum yield of lower boiling point hydrocarbons.

The bituminous materials processed in the presence of the hydrocarbons are substantially deprived of their hydrocarbon content and devolatilized in the process of my invention so that the coke from the bituminous material is intimately mixed and consolidated with the oil coke. A coke product results which has for the main part sufiicient body, strength and burning qualities so that no briquetting treatment is ordinarily required.

Among further objects of my invention is to provide a process where bituminous materials and hydrocarbon oils aresimultaneously converted and carbonized in one operation or step rather than in separate steps as in the carbonization process and in the separate cracking of the tar products from the carbonization operation. In-

creased yields and improved products result from the carbonization of the several operations with a minimum formation of gaseous products.

My invention in its specific embodiment consists in the use of stabilizing means when :processing mixtures of bituminous materials and hydrocarbon oils so that suspensions of such ma-' terials will not separate prior to their introduction into the process or during the process. Suspension of such materials would ordinarily the maintained prior to introduction into the conversion plant by some form of agitation. After introduction into the plant, maintenance of the suspension would be dependent on physical factors such as velocity conditions, turbulence, proportions of the components, relative specific gravity, surface tension, etc., factors which assume little importance in maintaining uniform and stable mixtures in my process. Advantages result from the stabilization of these mixtures as carried out in my invention since in addition to stabilizing same, the suspensions retain their uniformity and are in a suitable condition to also maintain in suspension catalytic materials which, in many cases even though in very finely divided state, are heavy and readily separated out.

The stabilization is brought about by the use of a paste consisting of an admixture of colloidal clay and water into which a salt is preferably incorporated which, when emulsified with the oil, will prevent the oil suspension containing dispersed coal from breaking. Other stabilizing agents, such as soaps, gums, glues, etc. may be used alone or in conjunction with the clay. The incorporation of a soluble salt, such as zinc chloride, for example, causes a thickening of the oil mixture and assists in the stabilization of same. Some salts added for this purpose also exert a catalytic eifect upon the subsequent conversion reaction. When other catalysts are used, the emulsion assists in stabilizing the resulting suspension. The proportion or quantity of bituminous materials which can be admixed with the oil in this manner depends on the fineness of pulverhydrocarbon oils as above prepared to cracking or conversion conditions at elevated temperaturesv in some, form of conversion apparatus of which the attached drawing is an illustration.

Temperature conditions used, at the outlet of the heating element may vary from 700 to 1200 F., and pressures may vary from atmospheric to high super-atmospheric pressures.

Pressure-on the balance of the system may vary from sub-atmospheric or atmospheric pressure to high super-atmospheric pressures.

Referring now to the attached drawing, the

stabilized suspension of bituminous material in hydrocarbon oil is introduced through line I and valve 2 and pumped by means of pump 3 through line 4 and valve 5, with valve 6 in line I closed, into line 8 where it mixes with hot refiux oil being pumped from the dephlegmator. This mixture of materials to be processed then passes into the heating element 9 located in the heating zone 10, the heating element being of such design as to process the oil suspension at suitable time, temperature, pressure and velocity conditions. The heated materials or products therefrom leave the heating zone through line H and valve l2 and enter the reaction zone 13 where the reaction continues and vaporization and separation or deposition take place. Materials withdrawn from this reaction zone during the period when the process is being brought to operating conditions or removed during the operation are withdrawn through line l4 regulated by valve l5 which may lead to storage or to suitable processing elements not shown. The vaporous and gaseous products leave the reaction zone through line 16 and valve I1, and enter near the bottom of a dephlegmating zone l8 where the vapors may be subjected to heat interchange and cooling. The reflux condensate and any materials added flow downward through the line 19 and valve 20 to the suction side of hot oil pump 2| from which they are pumped through line 8 to mix with fresh materials and be reprocessed. The vapors and gases leaving the dephlegmator l8 pass through the line 22 and valve 23 to the condenser and/or cooler 24 and the cooled products then flow through line 25 and valve 26 into the receiver 21 where separation of the liquid and uncondensed vapors and gases is efiected. The gases and uncondensed vapors leave the system through line 28 regulated by valve 29 and the liquid product containing motor fuel hydrocarbons is withdrawn through line 30 regulated by valve 3|. Water is withdrawn through line 50 regulated by valve 5|. Regulated portions of the oil product produced in the receiver 21 may be discharged through the line 32 and valve 33 to the suction side of pump 34 which pumps this oil through line 35 and valve 36 to the top of dephlegmator l8. During the starting up period or in the progress of the operation, hydrocarbon oil may be introduced through line 31 and valve 38 to the suction side of pump 39 from which it is pumped to the dephlegmator through lines 40 and 4|, valve 42 being open and valve 43 in line 40 being closed. A part of the flow of the hydrocarbon oil may be directed to the heating element 9 by partly opening the valve 43 and with suitable adjustment of valve 42 allowing said oil to fiow through line 40 and valve 44 into lines 4 and 8, the valve 45 in line 45 being closed, or the whole flow of the hydrocarbon oil may be pumped directly to the heating element by closing valve 42 and opening valve 43. In the event that it may be so desired, a portion or all of the oil may be directed through line 46 and valve 45 into the line I from which it can be directed into line I I before or after valve l2 by the obvious regulation of either valve 41 in line 48 or valve 49. In a like manner, any desired portion of the stabilized suspension of bituminous material in hydrocarbon oil may be pumped by pump 3 through line 4 and directed, if so desired through valve 6 in line 1 into the line H.

As a specific example of the application of the method of my invention and the results obtained, a smooth paste prepared from approximately one part of clay and 10 parts of water was agitated with approximately 14 to 16 times its own volume of 28-30 degrees A. P. I. gravity topped Mid- Continent crude oil and incorporated into same forming an emulsion. This emulsion was then stabilized by further agitation and the addition of approximately 34% of a 16 Baum zinc chloride solution, when a pronounced thickening effect was observed. Approximately 50% of powdered Illinois bituminous coil Was then stirred in and agitated with the emulsified oil and a stable, uniform and intimate suspension obtained. This product when used as a charging material to the process and treated in the heating coil together with recycled oil from the process so that the temperature and pressure at the heating coil outlet is approximately 920 degrees F., and 400 pounds should give the following results with an operation of the non-residuum type i. e. where there is no removal of non-vaporized oil from the reaction chamber after the process has been brought on stream and operating conditions fully established. In such operation the pressure is reduced in the line from the heating coil to the reaction chamber to approximately 125 pounds. The vapors from the reaction chamber are dephlegmated and partially converted hydrocarbons condensed and returned to the heating zone as recycled oil. The temperature at the top of the dephlegmator is maintained at about 450 degrees F., by recirculation of the end oil product. The pressure on the reaction, dephlegmation, condensing and collecting zones is regulated by maintaining a liquid level in the receiver and the release of the uncondensable gases formed during the operation.

The above described operation may be started and brought to substantially normal conditions of operating pressure and temperature by processing separately the 28-30 gravity topped crude only. This period covers a space of approximately 3 hours.

The blended coal and oil coke product removed from the chamber at the end of the run would be a broken agglutinated mass, quite dry, not quite as hard as petroleum coke and lacking to some extent in its honey-comb structure. The volatile content of the coke blend would be approximately 16% and the calorific value, about 13,500 B. t. u. per pound.

The distillate from the process would contain approximately 73% of 418 end-point motor fuel. The composite motor fuel would have an antiknock value equivalent to approximately 40% of benzol in Pennsylvania straight run gasoline. The distillate is calculated to be produced from the coal at the rate of approximately 12 gallons per ton and approximately 78% based on the topped crude oil processed. Yields of approximately 35% of motor fuel may be made from the mixture at the conditions of the above example.

My invention should not be construed as being limited to the examples which I have shown, or the-particular components and proportions of materials used, or the specific manner of preparation which I have given only by way of illustration since within the scope of the invention, there are many combinations and modifications that may be employed.

I claim as my invention:

1. A process of treating substantially solid comminuted pyro-bitumen, which consists in mixing said pyro-bitumen with an emulsion of water and oil containing zinc chloride and an emulsifying agent, and then subjecting such mixture to temperature sufiicient to decompose the same and comminuted pyro-bitumen, which consists in mixing said pyro-bitumen with an emulsion of water and oil containing zinc chloride and an emulsifying agent, and then subjecting such mixture to temperature and pressure sufficient to decompose the same and produce therefrom relatively low boiling hydrocarbons.

3. A process for treating hydrocarbon oil and solid pyro-bituminous material which comprises admixing the pyro-bituminous material in finely divided form with the oil, converting the mixture into a suspension by the incorporation of an emulsifying agent thereinto, thickening and stabilizing the suspension by adding zinc chloride thereto, subjecting the suspension to cracking conditions of temperature and pressure and separating the same into vapors and unvaporized residuum, and condensing the vapors.

4. A process for treating hydrocarbon oil and ,solid pyro-bituminous material which comprises admixing the pyro-bituminous material in finely divided form with the oil, incorporating a paste of colloidal clay and water into the mixture to form a. suspension, thickening and stabilizing the suspension by the addition of zinc chloride, subjecting the suspension to cracking conditions of temperature and pressure and separating the same into vapors and unvaporized residuum, and condensing the vapors.

ALFRED FISHER.