A method of enrichment of the fuel shale

 

(57) Abstract:

The invention relates to processing, fuel, petrochemical areas and can be used to enrich the fuel and raw materials, especially low-grade. The invention consists in that in the method of enrichment of the fuel oil shale, comprising the treatment agent, the formation and separation of liquid residue as a processing agent used crude oil and shale as a fuel used slates, dried to equilibrium moisture, and the treatment is carried out by filtration of the crude oil through the oil shale at a temperature of the processing agent is not higher than the temperature of the beginning of the volatile components. In addition, the process is carried out in temperature ranges from room temperature up to +50C. Technical result is an increase of ecological culture production while reducing energy consumption and simplify the method. 1 C.p. f-crystals, 1 Il., 3 table.

The invention relates to the field of fuel production from shale and may find application in oil shale processing, fuel and petrochemical industries.

It is known that in the future will increase the consumption of oil shale as an energy source and will razvivawciesja, woodworking and other industries. (Getting from oil shale fuel and non-fuel products. That Is, Gorlov, A. B. Wills-Epstein).

The known method of producing motor fuels from oil shale by semi-coking in the generators. (Zelenin N. And. Shale fuel. Costoptimized, 1948 S. 71).

Also known a method of producing motor fuel by interaction (thermal) with the solvent at temperatures from 400-430oC, a pressure of 30-50 bar and the ratio of the slate : solvent 1 : 1,3-2,0. The resulting distillate separated from the ash extract and consult last. While coke is separated from the liquid products (ed. St-in the USSR N 104264, CL 10 G 1/02, 1956).

The known method are somewhat different from the latter by the fact that the shale interaction with the solvent and ash coking of the extract are in the presence of polydimethylsiloxane, taken in an amount of 0.01-0.2% at 20oC (ed. St-in the USSR N 941396 C 10 G 1/04).

The disadvantages of these methods are the high energy costs, hazardous conditions due to high temperatures, the use of dangerous flammable substances.

Known also another way of exploitation of oil shale. Processing Slano the cooling and unloading nearly equal large quantities of spent shale.

However, this method is uneconomical in relation to shale, have low organic matter content.

The first patent on the processing of oil shale was obtained in 1694 in the UK. Later, many techniques were developed based on distillation in a retort, introducing improvements to the regeneration as much energy as possible, present in oil shale (patent of Russia No. 2049804, IPC C 10 G 1/04).

The disadvantages of these methods in the following: high energy consumption, the presence of olefins and heteroatoms in the resulting product. Attempts were made to circumvent the disadvantages and solution of this problem by the use of solvent extraction oil shale at room temperature.

In Israel patent N 51676 describes a method for the fuel gas and hydrocarbon from the carbonate-bearing shale. According to this invention, oil shale is subjected to distillation in a retort at a temperature of approximately 500oC through combustible gases, which contain mainly hydrogen, CO2, CO and steam. Then the residual consolidatasi gravel is heated at a temperature of 1100oC in the presence of steam and air, the remainder of which were thrown away in waste.

A known method of obtaining a carbon-containing briquettes (patent RF N 2096442, C 10 L 5/04, 5/10, 5/30 ), including the initial drying wet shredded fuel material (coal coke breeze, peat, wood waste), mixing it with a binder (lignosulfonate, liquid glass), briquetting the mixture, the heat treatment of the briquettes at 200-700oC and cooling them.

The disadvantages of this method is that no additional enrichment of the combustible organic substances, high temperature heat treatment of the briquettes, the complexity of the operation of the cooling of hot briquettes in a drum mixer. Therefore, this method may serve only as a distant analogue of the claimed invention.

There are a number of publications (authors - Wills-Epstein A. B., and others) related to the processing of oil shale including a high amount of mineral components, low organic matter content, for example, the log input: Chemistry of solid fuels, so-14, 2, S. 67-70, 1980. The publication summarizes a series of experiments processing of the Baltic oil shale. Presents methods of processing oil shale, the mechanism of which is reduced to the destruction of the organic matter present in the oil shale, the report noted, this extract is useful as a fuel for the engine or power unit, as raw material for coke production, etc. Separation of the final products produced by distillation.

The disadvantages of this method is the high energy cost because of the oil shale to a temperature of 400-430oC for 6-10 h at pressure of 30 to 50 atmospheres in the presence of a solvent which has a boiling point in the range from 210 to 340oC. in Addition, the critical conditions for the safety of personnel requiring high quality and low environmental quality of the work inherent in technology solutions for the processing and refining of shale - boiling solvent, high temperature heating of oil shale up to 430oC, large amounts of waste, small - useful product serious shortcomings of the claimed methods, making you look fundamentally different approaches.

Closest to the proposed method is a technology joint thermal cracking of oil shale (for example, sapropelite) and oil tar oil (residual oil) (RF patent N 2009162, C 10 G 9/10 ). During thermal cracking of heavy oil feedstock from shale processesa for the preparation of raw materials through the use of techniques of varying the degree of polydispersity and kinetic stability of the reaction system. This technology includes the following basic stages:

the mixture of residual oil feedstock, and in the case of thermal hydrocracking of tar and risaykl (so Kip. above 370oC), with shredded combustible shale with obtaining a paste;

thermocracking or thermal hydrocracking paste in the hollow reactor;

the separation of the solid product from the liquid by centrifugation or vacuum distillation;

distillate ash-free liquid products of thermal cracking units or thermal hydrocracking.

Schematic diagram and material balance of thermal cracking units tar with oil shale is shown in the drawing.

During thermal hydrocracking of tar mixed with risaykl (ratio of 1 : 0.2 to 0.4) and the Baltic oil shale (15%) under a pressure of 10 MPa and a temperature of 425oC is reached deep conversion of heavy crude oil in the gasoline fraction with so Kip. 200oC and diesel fraction with so Kip. 200-370oC - the total yield of 90% and above. An important advantage of the method is the possibility of thermal hydrocracking without expensive catalysts and at a relatively low pressure (3-5 MPa) and thermal cracking units without hydrogen. It is possible to reduce capital and operating at the high temperature, the need for the use of the autoclave, a large solid waste materials, the complexity of technology.

The task of the invention is to develop enrichment method shale high economic and environmental level while reducing waste and simplifying technology.

The essence of the invention lies in the fact that in the method of enrichment of the fuel shales, including the processing of the raw product, the formation and separation of the liquid residue, preparation of raw produce moisture measurement and bringing it up to the equilibrium value of drying, and as a processing agent used crude oil. The treatment is carried out at a temperature of the processing agent is not higher than the temperature of the beginning of the release of volatile oil components by filtering it through the slate.

Furthermore, the method is carried out in the temperature range from room temperature up to +50oC. It is the best temperature regimes.

The method is as follows.

Slate regardless of field and depth is controlled by a check on the humidity. Then bring it to the values of equilibrium moisture content, usually not more than 3 wt.% in relation to the total weight of SNIA completely dehydrated shale may although it is inconvenient and causes additional costs of energy and heat. Drying the humidified raw material can be performed by any method: under favorable weather conditions the summer period is directly under the open sky or under a canopy in the presence of precipitation. Then the slate even layer stack on glass, metal, ceramic or made of another, resistant to oil, filter material, located inside the tank for carrying out the method. Capacity for oil is also made from a material resistant to it. The recommended height of the layer of shale in the unit it is recommended that no more than the maximum length of the fuel briquette, which can be obtained. The size of the particles stacked layer of slate can be different depending on the type of equipment available to the user. Very small particles of dust type < 0.1 mm is not only easy to use (dust, pollution), but also ineffective in the process of interaction of shale oil because of the low permeable (filter) ability due to lack of transport pores for the passage of the processing agent. Then in the tank serves the oil to pass the enriched product and to increase the production and operation of fuel briquettes. The amount of oil is installed at the beginning of the technical process by the first portions of the processed products. The criterion for the adequacy of the quantity of the supplied oil is the lack of drops flowing from the processed product. We need to do is extract the processed shale at diafragmirovanija pallet for a possible runoff of excess oil. For this you can use another tank. Excerpt saves oil, increases production, because the residues are returned to the process. For achieving the desired characteristics of the enriched product is fed to the briquetting and packaging. Depending on the upcoming conditions of transportation and storage selected binder and film materials for packaging briquette. Specific examples confirming the effectiveness of the inventive method enrichment shale deposits, are presented in table. 1.

The inventive method simultaneously enriched shale refines the oil due to its treatment by filtering through a layer of shale (see tab. 2). Enriched with more than boiling and more depleted magelonidae components filtered oil with a lower viscosity traveo way - practically no waste and its high ecological culture.

The temperature of the enrichment process of the slate by filtering oil through it, as a rule, is within(+5)-(+50)oC. Conduct of the enrichment process of shale oil at a temperature above the 50oC is not recommended due to possible evaporation of volatile toxic and flammable products from the oil. The implementation process at temperatures below +5oC is difficult due to a significant increase in the viscosity of the oil, reducing the efficiency of the enrichment, and the possibility of phase separation system with falling ice crystals. Recommendations on quantities used pressures justified by the savings in energy use. Therefore, it is expedient processing of oil shale carried out at atmospheric pressure.

This method allows the use of shale oil and different fields (see table). Particularly promising application of the claimed technology in regions where both occur and shale oil, as for example the territory of Saratov, Samara, Volgograd and other areas. Problems of subsistence (non-conforming) oil and inefficient shale allow to solve the fuel is not only NGOs, local fuel and inexpensive. NCV Volga shale enriched with oils, depending on the field last may reach values of 10.7-12.9 MJ/kg (GOST 7917-81), which is much higher specific heats of combustion of raw shale concluded within 6,8-of 9.3 MJ/kg This indicates the increase in fuel condition processed shale.

Projected reserves of oil shale only in the European part of Russia is 56 billion tons, and studied the Volga basin - 43% of total reserves, therefore, the high relevance of the development of environmentalists Cesky acceptable enrichment technologies shale without the high cost of energy in these processes.

The method was tested in laboratory conditions and in the conditions of specific fields of Saratov and Samara regions.

1. A method of enrichment of the fuel oil shale, comprising the treatment agent, the formation and separation of the liquid residue, characterized in that the processing agent used crude oil, train oil shale moisture measurement, as well as fuel and oil shale used slates, dried to equilibrium moisture, and the treatment is carried out by filtration of the crude oil through the oil shale p is the procedure under item 1, characterized in that the process is carried out in the temperature range from room temperature up to +50oC.

 

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