A method of processing oil shale

 

(57) Abstract:

Usage: petrochemistry. The inventive shale is subjected to thermal decomposition to obtain the vapor-gas mixture of liquid and gaseous components. The total gas-vapor mixture is subjected to catalytic treatment in a fluidized bed or fixed bed of the catalyst, which is used as the iron-containing acid contact type - polyphosphate iron xerogels patterns in the amount of 20-80 wt.% shale, containing 95% polyphosphate iron with a ratio R2ABOUT5:Fe2O3=0,5, the rest is water (1), or a composition of two catalytic contacts in the amount of 40 wt.% shale (20% iron pin (1) and 20% of industrial Al-Ni-Mo catalyst with iron polyphosphate can be modified with metals - socialization - (R2O5+ Fe2O3+ MenOm) - 95%, where IUnABOUTm- oxides of the metals Mo, Co, Ni, Cr, V, si, and the process is carried out at 500-600oWith, or total gasoline fraction after its separation of the liquid products of thermal decomposition of oil shale in the presence of iron-bearing contact (1) and the hydrogen-containing gas at temperatures 340-400oWith the pressure in the3. Effect: improved quality of liquid products. 5 table.

The invention relates to the field of production of commodity fuel and chemical products and semi-products of the processing of natural oil shale with the aim of obtaining products of organic synthesis, shale resin semi-coking and motor fuels, similar to the results obtained from crude oil, namely gasoline /1 Rudin M,, Serebryannikov N. D. Directory of senseperception. -L.: Chemistry. 1988; 2. Feinberg Century C. the Resin of the Baltic oil shale as chemical raw materials. -L., 1986/.

Commercial gasoline during the processing of oil shale do not receive. It is known that the processing of oil shale on installation with solid heat carrier UTT-3000 (Estonia, Narva) receive the following liquid products: heavy oil 40,26 wt.%, the average oil 37,32 wt.%, light oil are 22.42 wt.% (including: gasoline fraction -12,61 wt.% and turbine fuel 9,81 wt.%). The gasoline fraction produced from the products of thermal processing of oil shale by fractionation at temperatures of boiling and condensation with subsequent treatment using the methods of the sulfuric acid purification and catalytic treatment in the presence of polymerizes catalysts /3. Chemical technology is rastvorimykh C1-C3alkylresorcinol. Queen N.In., Solodovnikov N. Century ; 5. Petroleum products //Handbook edited Losikova B. C.-M. : Chemistry. 1966/. However, these methods of obtaining gasoline from shale do not provide a stable commercial product.

The disadvantages of these processes are their low efficiency, multistage and technological challenges of the implementation process. The resulting gasoline contain large amounts of unsaturated and hetero-organic oxygen - and sulfur-containing compound have a low octane number and are extremely unstable.

Closest to the proposed invention is a method of processing oil shale lies in their thermal decomposition of obtaining gas mixture of liquid and gaseous components, heat treatment gas mixture, condensation and fractionation of components. You get a marketable product - gasoline (6. Patent 2094447 the Method of thermal processing of sulfur shale. Saratov state technical University). Thermal treatment is carried out by pyrolysis at T=550-575oIn the presence of a catalyst containing SiO278%, CR2ABOUT318%2About 4%. In resultone

The present invention is the selective removal of oxygen - and sulfur-containing compounds with preservation of hydrocarbon raw materials, reduction of unsaturated compounds included in the composition of the liquid products, and produce marketable products and intermediate semi-products from oil shale for the production of motor fuels, including gasoline.

The task is achieved by thermal decomposition of oil shale with getting gas mixture of liquid and gaseous components using catalytic processing, condensation and fractionation of components boiling temperatures, while catalytic processing is subjected to the total gas-vapor mixture in a fluidized bed or fixed bed of the catalyst, which is used as the iron-containing acid contact type - polyphosphate iron xerogels patterns in the amount of 20-80 wt.% shale, containing 95% polyphosphate iron with a ratio R2ABOUT5:Fe2ABOUT3=0,5, the rest water (1), or a composition of two catalytic contacts in the amount of 40 wt.% shale (20% iron pin (1) and 20% of industrial Al-Ni-Mo catalyst), polyphosphate iron can be Modific what ABOUTm- oxides of the metals Mo, Co, Ni, Cr, V, si, and the process is carried out at a temperature of T=500-600oC. Or catalytic processing is subjected to total gasoline fraction after its separation of the liquid products of thermal decomposition of oil shale in the presence of iron-bearing contact (1) and the hydrogen-containing gas at temperatures 340-400oC, hydrogen pressure of 4-6 MPa, the space velocity of the feedstock 1-3 h-1the circulation of the hydrogen-containing gas 200-1000 m3/m3.

Comparative analysis of the prototype shows that the inventive method differs from the known: 1) process in the presence of a new type of catalyst - SalesOrderHeader contact acid type entered in the amount of 20-80 wt.% shale, or in the presence of a composition of two types of contacts in the amount of 40 wt.% raw materials (20% iron contact and 20% of industrial AMN catalyst); 2) it is possible to carry out thermal processing separately gasoline fraction and light oil; 3) achieve a high percentage of sulfur removal and oxygen from recyclable products; 4) reduced content of unsaturated compounds in the composition of the products and intermediates, while maintaining a high yield of products; the A.

Thus, the claimed method meets the criterion of "novelty."

A comparison of the claimed technical solution is not only the prototype, but also with other technical solutions allowed us to identify the features distinguishing the claimed solution to the prototype that allows to conclude that the criterion of "significant difference".

The method of producing catalyst

The catalyst was prepared by deposition of urea salts of iron from a solution containing a calculated amount of phosphoric acid and metal salts of acetalization: Mo, Co, Ni, Cr, Cu, Ti, at a molar ratio of phosphorous pentoxide to the iron oxide R2ABOUT5:Fe2ABOUT3=0,5. After maturation and aging of the gel formed xerogel phosphate, dried catalyst contains according to atomic absorption analysis autopolyploidy iron and metals-acetalization.

The catalyst, as follows from derivatographic analysis, thermally stable up to high temperatures, g at T=850oWith 10 wt.%. However, its use after regeneration is impractical because after annealing coke, as shown by x-ray and microscopic analysis, changing its phase composition, oxides gelee 1.

Download shale in an amount of 10 g (Wa=3,35%; ANDd=50,8%; conventional organic mass 34,21%) is heated to a temperature of 570oWith speeds of 70 deg/min. At a temperature of 570oTo download stand for 20 minutes.

Forming in the process of semi-coking gas-vapor mixture is fed to the catalytic treatment at a temperature of 500oC. as the iron-containing catalyst is used for the contact composition: base material - (R2ABOUT5: Fe2ABOUT3= 0,5) - 95%, the rest is H2About; the catalyst is modified by a number of metals-socialization - Me 2 wt. %. The amount of catalyst 40 wt.% on the slate. After the catalytic processing of the calibration gas is supplied to the condensation. Gaseous products are analyzed by gas chromatography. Liquid products are analyzed by methods group chemical, elemental analysis and gas-liquid chromatography.

The yield of liquid products is 25,09 wt.%, and the output ASG 29,59 wt.%. In the prototype, the output liquid is 10%, and recalculated the output of the ASG is to 30.5 wt.% [table.1].

Example 2. (without catalyst)

Compared with non-catalytic experience in the catalytic experience at a temperature of 570o the s 53,9%. Increasing the amount of hydrocarbons in the resin 10 wt.%. The content of asphaltenes ( high-molecular compounds containing oxygen and sulfur) can reduce almost to zero.

Therefore, the proposed method allows to increase the yield of liquid products compared to non-catalytic and experience with the prototype, in addition, it is possible to reduce the sulfur content while maintaining the basic structure of the hydrocarbon resin parts.

Obtained in the process the resin is then subjected to fractionation to obtain a gasoline fraction.

In table. 1 shows comparative data substantiating identified distinctive characteristics and proving the positive effect of the proposed method.

In table. 2 shows changes in the fractional composition of the liquid products obtained in the catalytic and non-catalytic experiments.

In table. 3 presents comparative data characteristics of the resulting gasoline fraction.

Examples 3-6.

The data presented in the table.1, show that the introduction of the catalyst in amount less than 40 wt.% shale, for example, in the amount of 20%, the yield of liquid products is 17.50 wt.% (experiment 3), and the degree udaleniya wt.%, and the output of the gas is increased by 10.2 wt.% (6). The degree of sulfur removal from the products is 62,50%.

Data of gas composition are presented in table. 4.

Thus, in the concentration range of the catalyst 20 to 80 wt.% shale catalytic effect is achieved, which allows to increase the yield of liquid products and to reduce the sulfur content in the mixture of resin products, including gasoline fraction, compared with the prototype and non-catalytic example (Example 2).

Examples 7-9.

In the temperature range 500-600oWith the maximum yield of liquid is achieved at T=570oWith, as in the prototype, which allowed us to choose this temperature for a further catalytic experiments.

Examples 10-11.

Shows the reusability of this catalytic contact. So using the experience of the catalyst after 6 hours was restored in a stream of hydrogen at a temperature of 500oC for 4 hours, allows to obtain a high yield of liquid products 24,9 wt.% (experiment 10), and the degree of sulfur removal is achieved 55,5%. Using the experience of the catalyst after regeneration and recovery in the current of water is S="ptx2">

Thus, the possibility of repeated use of the catalyst before and after regeneration without appreciable loss of activity.

Examples 12-13.

When used in the process of industrial AMN catalyst the yield of liquid is reduced by 9,49% and 15.6 wt.% (experiment 12), the degree of sulfur removal 53,9%. In the process, the catalyst rapidly loses its activity. And when used in the process of AMN catalyst after 6 hours the yield of liquid is reduced to 13.7 wt.%, output of gas, and the degree of sulfur removal is 37.5 per cent.

Thus, the use of industrial AMN catalyst is impractical, because the catalyst is rapidly deactivated.

Example 14.

The use of the composition of two catalytic contacts in the amount of 40 wt.% raw materials (20% iron contact and 20% of industrial AMN catalyst) gives almost the same effect as when using ASM catalyst, but it is possible to reduce the number of unsaturated compounds included in the composition of the hydrocarbon resin parts, as well as sulfur-containing compounds, and to increase the stability of the contact.

Thus, about risotti iron contact acid type.

The results show that the implementation process by thermal processing gas to specified contacts allows for a high yield of liquid products selectively remove sulfur and oxygen from the composition of the products, to make partial hydrogenation of unsaturated compounds. Obtained from the resin of the gasoline fraction can be used as an intermediate and exposed to a secondary catalytic processes in order to produce a marketable product using conventional catalysts.

2. Thermal processing of the gasoline fraction in the presence of hydrogen.

Apart from getting gasoline fractions by catalytic thermal treatment of the total gas mixture products of the process of thermal decomposition of oil shale, it is possible to carry out thermal treatment selected from CBC total gasoline fraction or fractions of light oil in the presence of hydrogen.

Example 1.

The experiment was performed in the setting of continuous operation. Gasoline fraction, the characteristics of which are presented in table.5, are mixed in a mixer with hydrogen and the mixture was fed into the reactor. The volumetric feed rate 2H-1, obiora, the amount of catalyst 60 cm3. As the iron-containing catalyst is used in contact with acidic type of composition:

base material - (R2ABOUT5:Fe2ABOUT3=0,5) - 95%, the rest is H2O; catalyst modified a number of metal-socialization - Me 2.0 wt.%. Heating of the reactor is carried out using a furnace. The temperature in the reactor 380oC.

Formed during the calibration gas after the catalytic processing is supplied to the condensation. Liquid products are analyzed by methods group chemical, elemental analysis and gas-liquid chromatography.

The yield of liquid products is 93.2%, gas to 6.8%. The content of unsaturated hydrocarbons is reduced by 30.7% to 14.3 wt.%, iodine number is reduced to 12.5 mg2/100, the Degree of sulfur removal is 77,9%, the sulfur content in the resulting product of 0.28 wt.% [table. 5].

Thus, the proposed method allows for a small effect of gas and a high yield of liquid products to carry out the processes of selective hydrogenation of unsaturated hydrocarbons and destruction of hetero-organic compounds. Thus obtained gasoline fraction may further be subjected to the on gasoline.

Examples 2-3.

The use of iron-containing contact:

base material - (R2ABOUT5: Fe2ABOUT3=0,5) - 95%, the rest is H2O (experiment 2) allows you to change the composition of the resulting gasoline fraction. The yield of liquid products is 90,2%. The content of unsaturated hydrocarbons is reduced by 21.9 wt.%, iodine number gasoline fraction obtained 32 mg I2/100, the Degree of sulfur removal is 42,5%, sulfur content to 0.73 wt.%.

The introduction of the iron contact additional metals-socialization affects the activity change of the contact. About the activity of the catalyst in the process is judged by the degree of sulfur removal from recyclable raw materials and the degree of hydrogenation of unsaturated compounds. With the introduction of the catalyst composition of molybdenum in the amount of 0.015 wt.%(experiment 3) number of unsaturated hydrocarbons is reduced by 15.9 wt.%, iodine number is 25. The degree of sulfur removal 58,3%. The yield of liquid products is 96,6 about. %.

Thus, variation of the composition of the catalyst increases the catalytic activity of contact during thermal processing CBC total gasoline fraction. Ispstart partial hydrogenation of unsaturated hydrocarbons and to obtain thus a gasoline fraction with improved processing characteristics.

Examples 4-5.

We use ASM catalyst can significantly reduce the content of unsaturated hydrocarbons (experiment 4). Iodine number obtained gasoline fraction is reduced to 0.5. The yield of liquid products was 94.9 wt.% The sulfur content is reduced to a 0.59 wt.%, the degree of sulfur removal of 53.5%. However, in the process of AMN catalyst rapidly loses its activity. So, when using the process of the catalyst after 6 hours the degree of sulfur removal is significantly reduced and is 37%, a sulphur content of 0.8 wt.% (experiment 5). Iodine number increased to 9.8. The yield of liquid is reduced to 65%.

Thus, the use of industrial AMN catalyst in the specified process is impractical.

Examples 6-7.

The process at a temperature of 340oWith (6) shows that the yield of liquid products is lower than 380oC. Increase the process temperature up to 400oC leads to a decrease of the yield of liquid.

Thus, the maximum catalytic effect is achieved in the temperature range 340-400oAt a process temperature of 380oC.

Examples 8-9.

The variation of the volumetric feed rate of hydrogen affects treason and hydrogen 200 m3/m3allows to obtain a gasoline fraction with a high iodine number (experiment 8). Increasing the space velocity of hydrogen to 1000 reduces the value of iodine number, but this reduces the yield of liquid products (experiment 9).

Thus, in the range of volumetric flow rates of hydrogen 200-1000 m3/m3the maximum catalytic effect, allowing 30.7 wt. % reduction in the content of unsaturated hydrocarbons and 78% reduction in the sulfur content in the gasoline fraction obtained.

Examples 10-11.

The variation of the volumetric feed rate of the raw material affects the change of the yield of liquid products, their composition, and changes in the ratio of hydrogen: feedstock.

Reducing the space velocity of the raw material up to 1 h-1(experiment 10) leads to a decrease of the yield of liquid. This reduces the iodine number and the content of sulfur in the composition of the obtained gasoline fraction. Increasing the space velocity of the raw material also leads to a lower yield of liquid products. However, this also increases the value of iodine number and decreases the degree of sulfur removal.

Thus, the maximum catalytic effect is achieved in the range of volumetric speed and pressure in the range of 4-6 MPa will get almost similar results on the degree of removal of organic sulfur compounds, the yield of liquid products and the change in iodine number.

Thus, in this range of pressures is achieved comparable catalytic effect.

Examples 14-15.

When used in the process spent catalyst (experiment 14) receive results similar to experiment 1, indicating a slight decrease in the activity of the catalyst in the process.

Test data activity of the regenerated catalyst in the process (experiment 15) show that its activity is somewhat lower than the original contact.

Thus, the possibility of multiple use of this catalyst in the specified process.

The results show that exposing thermal processing CBC total gasoline fraction, you can significantly reduce the content of unsaturated and hetero-organic compounds. Thus obtained gasoline fraction may then be subjected to a secondary catalytic processes in petroleum refining, using traditional catalysts for these processes.

Thus, the use of the claimed methods on p. 1 and p. 2 will allow to produce gasoline from slanchevi a mixture of liquid and gaseous components, with the use of catalytic processing, condensation and fractionation of components boiling temperatures, characterized in that the catalytic processing is subjected to the total gas-vapor mixture in a fluidized bed or fixed bed of the catalyst, which is used as the iron-containing acid contact type - polyphosphate iron xerogels patterns in the amount of 20-80 wt. % shale, containing 95% polyphosphate iron with a ratio R2ABOUT3: Fe2O3= 0,5, the rest water (1), or a composition of two catalytic contacts in the amount of 40 wt. % shale (20% iron pin (1) and 20% of industrial Al-Ni-Mo catalyst), while iron polyphosphate can be modified with metals-socialization (P2ABOUT5+Fe2ABOUT3+MenOm) - 95%, where IUnABOUTmthe oxides of the metals Mo, Co, Ni, Cr, V, si, and the process is carried out at 500-600oWith, or total gasoline fraction after its separation of the liquid products of thermal decomposition of oil shale in the presence of iron-bearing contact (1) and the hydrogen-containing gas at temperatures 340-400oC, hydrogen pressure of 4-6 MPa, the space velocity of the feedstock 1-3 h-1circulation vodorodozapra the

 

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