RU2733399C1 - Method of producing hydrocarbon products - Google Patents

Abstract

FIELD: bioenergetics.

SUBSTANCE: invention relates to production of hydrocarbon products from bio-alcohol produced from plant biomass. Proposed method comprises the following steps: first intermediate product—natural gas—second semi-product—nitrogen-containing mineral fertilizers, which are introduced into soil during the vegetation period of crops for production of crop production products—third semi-product, wherein the harvesting part of the crop is processed or sold to the consumer, and non-standard part and green mass are directed to stage of biochemical treatment—hydrolysis, where after rectification separation and purification hydrocarbon component is obtained in form of ethanol-containing mixture in vapor phase—fourth semi-product, as well as production wastes; then said ethanol-containing mixture in vapor phase after additional purification is directed for catalytic processing into gaseous and liquid hydrocarbon products with composition close to natural oil and gas products—fifth semi-product, from which part of gaseous products are processed into natural gas and returned to the stage of producing nitrogen-containing mineral fertilizers, and remaining part of said gaseous products and liquid hydrocarbon products are realized as end product.

EFFECT: technical result is creation of closed extended cycle of production of hydrocarbon products from bioethanol obtained from plant biomass.

4 cl, 1 dwg, 4 tbl

Description

The technical field to which the invention relates

The invention relates to the field of bioenergy, in particular to a method for the production of hydrocarbon products, such as gasoline or diesel fuel, from a bio-alcohol obtained from plant biomass.

State of the art

The threat of an energy crisis associated with the depletion of fossil fuels is forcing scientists around the world to search and develop alternative renewable energy sources. One of these renewable and environmentally friendly sources is the sun - a participant in the process of plant photosynthesis. As a result of this process, carbon dioxide is converted into green plant matter (biomass), which can be used as biofuel by producing liquid combustible substances (bioethanol, biodiesel, biomethanol).

Of all types of liquid biofuels, bioethanol, obtained from raw materials rich in starch and sugars, is the most widespread.

The most promising raw material for bioethanol production is plant raw material (lignocellulose), which does not represent nutritional value for humans, the so-called raw material of the second generation, namely, residues of cultivated plants (wheat straw, corn, rice, sugarcane bagasse). The use of such raw materials allows, with a known use of crop yields, to obtain an additional product from non-food waste.

Traditionally bioethanol is used as an additive to gasoline in various ratios (E5, E10, E85 E100) or as an additive to gasoline (5-15%). This can significantly reduce the emissions of pollutants from combustion. Nevertheless, the complete replacement of traditional fuel with bioethanol is difficult because it requires modification of automobile engines to run on pure ethanol and the volume of the gas tank to maintain the average vehicle mileage due to the lower energy content of ethanol compared to gasoline. In addition, ethanol is highly volatile due to its high vapor pressure and is highly hygroscopic.

Due to the aforementioned shortcomings, in recent years, the attention of researchers has been focused on the development of a technology for the catalytic conversion of bioethanol with the production of gasoline hydrocarbons into motor fuels.

Thus, it is known to use high-silica zeolites of the HZSM type as catalysts for the continuous production of aromatic hydrocarbons. The specific average pore diameter of these zeolites prevents the formation of hydrocarbons with a number of carbon atoms in the molecule greater than 12, which ensures high selectivity of the process of converting ethanol into aromatic and aliphatic hydrocarbons of various structures.

The closest analogue of the claimed invention is a method for producing liquid hydrocarbon products from bioethanol obtained as a result of processing biomass of plant raw materials, followed by obtaining motor fuel [Tretyakov V.F. et al. Catalytic conversion of bioethanol into hydrocarbons / Bulletin of MITHT, 2010, T. 5, No. 4, p. 77-86]. The conversion of bioethanol is carried out in a flow reactor, while the highest yield of liquid hydrocarbons was achieved when using high-silica zeolites of the HZSM-5 type, synthesized using hexamethylenediamine (CKE-G), as well as promoted by zinc and iron, with a composition of 3% Zn / 27% Al ₂ O ₃ / Fe-CCE-G 50 (Si / Fe = 550) at a temperature of 350-420 ° C, a pressure of 0.1 to 10 MPa and a volumetric flow rate of 1-2 h ^-1 . To use the obtained hydrocarbon products as gasoline fuel, the obtained fraction of aromatic compounds is hydrogenated in an autoclave type reactor with a volume of 250 cm ³ on Rh, Pt-containing catalysts at a temperature of 250-300 ° C and a pressure of 10 MPa.

The disadvantages of the technical solution indicated as the closest analogue are the periodicity of the process, the lack of isolation (reproduction) and the possibility of expanding the production cycle, as well as the lack of accounting for the use of nitrogen-containing mineral fertilizers to obtain plant biomass.

Disclosure of the essence of the invention

The technical problem was the organization of a closed multistage technological scheme for obtaining hydrocarbon products from environmentally friendly sources.

The technical result consists in the creation of a closed extended cycle for the production of hydrocarbon products from bioalcohol obtained from plant biomass.

The technical problem is solved and the technical result is achieved in the present invention. A method for the production of hydrocarbon products from bio-alcohol obtained from plant biomass is proposed, including the following stages: from the first intermediate product - natural gas, the second intermediate product is obtained - nitrogen-containing mineral fertilizers, which are introduced into the soil during the growing season of agricultural crops to obtain a crop of crop products - the third intermediate product, at the same time, the conditioned part of the crop is processed or sold to the consumer, and the substandard part and green mass are sent to the stage of biochemical processing - hydrolysis, where, after rectification separation and purification, a hydrocarbon component is obtained in the form of an alcohol-containing mixture in the vapor phase - the fourth intermediate product, as well as production waste; further, the specified alcohol-containing mixture in the vapor phase, after additional purification, is sent for catalytic processing into gaseous and liquid hydrocarbon products with a composition close to natural oil and gas products - the fifth intermediate product, of which part of the gaseous products is processed into natural gas and returned to the stage of obtaining nitrogen-containing mineral fertilizers, and the remainder of these gaseous products and liquid hydrocarbon products are sold as the final product.

In one of the particular cases of implementation of the claimed method, the obtained gaseous and liquid hydrocarbon products are "artificial" gas or oil, similar in their properties to natural oil and gas products.

In one of the particular cases of implementation of the claimed method, the final product is commercial gasoline or diesel fuel.

In one of the particular cases of the implementation of the claimed method, the production waste from the hydrolysis stage is used as organic fertilizers or additives to animal feed.

Brief Description of Drawings

FIG. 1 shows a block diagram of expanded production of hydrocarbon products. FIG. 1 the following block designations are used:

1 - production of nitrogen-containing mineral fertilizers;

2 - agricultural production (crop production);

3 - biotechnological production of hydrocarbon (HC) solutions (hydrolysis plant);

4 - production of organomineral fertilizers, accompanying organomineral substances and products;

5 - transfer of liquid hydrolysis HC solution into the vapor phase by means of rectification and conversion of HC product in the vapor state on the catalyst into gaseous and liquid HC products with a composition close to natural oil and gas products;

6 - seed natural gas for the production of nitrogen-containing mineral fertilizers, the return of natural gas to the stream of recycling of HC products;

7 - auxiliary materials for the production of mineral fertilizers;

8 - dumping waste from the production of nitrogen-containing mineral fertilizers into the production of organic fertilizers;

9 - use of solar energy;

10 - solar flux - energy source of photosynthesis;

11 - sale of conditioned grain (processing or sale);

12 - flow of non-food agricultural residues (green mass) and substandard grain for biotechnological processing;

13 - discharge of crop waste into the production of organic fertilizers;

14 - supply of reagents to hydrolysis production;

15 - wastes from hydrolysis production;

16 - discharge of waste from hydrolysis production into the production of organic fertilizers;

17 - flow of HC solutions;

18 - the sale of HC products into substances required by the consumer.

Implementation of the invention

Each block shown in FIG. 1 scheme.

In the first block (1), first of all, seed natural gas (6) is fed - the first intermediate product, which ensures the start of the production of hydrocarbon substances, which is a product of the gas production or gas processing industry, as well as auxiliary substances (7) which can be nitric acid, ammonia, dioxide carbon, extraction phosphoric acid, potassium chloride and other substances, depending on the type of fertilizer produced. As a result of known technologies, nitrogen-containing mineral fertilizers (the second intermediate product) are obtained, for example, such as ammonium nitrate, carbamide, NPK fertilizers, as well as production wastes (8) that enter the organomineral fertilizers production unit (4).

The second block (2) is agricultural production (crop production), i.e. growing and harvesting agricultural crops (corn, sunflower, wheat) is the third intermediate product using solar energy in the process of plant photosynthesis (9) from the solar flux (10), as well as nitrogen-containing mineral fertilizers obtained at the first stage. At the same time, the obtained conditioned grain (11) is sold in a traditional way (processing or sale), inedible agricultural residues (green mass) and substandard grain (12) are sent to the third block of biotechnological processing (3), and crop waste (13) is sent to the production stage organomineral fertilizers (4).

The third block (3) is the biotechnological production of hydrocarbon-containing solutions (17) through the hydrolysis of agricultural residues of crops (green mass) and substandard grain obtained at the second stage of the scheme (2), where the necessary reagents (14) are also fed, in particular, acids, bases , microflora. Waste from hydrolysis production can be used as additives to animal feed (distillery stillage) (15) or discharged into the production of organomineral fertilizers (16).

The fourth block (4) is the production of organomineral fertilizers and related organomineral substances and products (lawns, enriched garden soil, flower soil) from the waste of the production of mineral fertilizers (8), plant growing (13) and hydrolysis production (16).

The fifth block (5) is a stage of converting a liquid hydrolysis hydrocarbon-containing solution (17) into a hydrocarbon component in the form of an alcohol-containing mixture in the vapor phase - the fourth intermediate product by means of rectification separation with further purification. Further, the specified alcohol-containing mixture in the vapor phase, after additional purification, is sent for catalytic processing into gaseous and liquid hydrocarbon products with a composition close to natural oil and gas products - the fifth intermediate product, from which part of the gaseous products is processed into natural gas (6) and returned (recycled) to the first block (7) for the production of nitrogen-containing mineral fertilizers, thereby replenishing the costs of natural gas (CH ₄ ) for their production, and the rest of these gaseous products and liquid hydrocarbon products (18) are sold as substances required by the consumer (for example, commercial gasoline, diesel fuel, ethylene, divinyl, biohydrogen, etc.) - the final product.

The stages considered have been tested and use technologies that are used in large-scale production of chemical, agricultural, biotechnological and a number of other industries and produce natural gas, mineral and organomineral fertilizers, agricultural crops, bio-alcohol, hydrocarbon products and others as the final product that meet regulatory requirements. The processes are carried out in well-known equipment, design tests of the equipment are drawn up and examined in detail from a financial and economic point of view. Therefore, the results of the work of individual units, the assessment of the quality of their work, the reliability of cost coefficients and the output in finished products are well studied and are known from the prior art.

The following examples illustrate the implementation of the proposed method.

Let us consider the first block for obtaining nitrogen-containing mineral fertilizers (see Table 1). For example, ammonium nitrate and urea were chosen as fertilizers.

For the production of ammonium nitrate, ammonia is used, which in turn is synthesized from a nitrogen-hydrogen mixture on an iron catalyst at temperatures of 380-450 ° C and a pressure of 250 atm. The main raw material for obtaining a nitrogen-hydrogen mixture is natural gas, the average consumption of which for the production of 1 ton of 100% NH ₃ for technology I (AM-70, AM-76, TEC) - 1174 nm ³ and for technology II (Chemico) - 1277.5 nm ³ [Information and technical guide to the best available technologies ITS 2-2015 "Production of ammonia, mineral fertilizers and inorganic acids". - M .: Bureau NDT, 2015]. For clarity of further calculations, the consumption of natural gas for technologies I and II is averaged, which is equal to 1226 nm ³ . The resulting gaseous ammonia is sent to the stage of neutralization of nitric acid with a concentration of 56-60% Mg (monohydrate) HNO ₃ , with further granulation of the resulting melt, carried out on one of the AC-72M, AC-72, AC-60, AC-67 units. The consumption of starting reagents for all aggregates is also averaged (see Table 1).

Urea is synthesized from ammonia and carbon dioxide at high pressure and temperature according to the following technologies: with full liquid recycling, which include Stamicarbon (AK-70) with full or partial reconstruction URECONR2006, Stamicarbon (AK-70) with an open cycle without improvements, TEC, and also on technologies of stripping in a current of СО ₂ , auto-stripping (in a current of NH ₃ ), Tecnimont [Information and technical guide to the best available technologies ITS 2-2015 "Production of ammonia, mineral fertilizers and inorganic acids". - M .: Bureau NDT, 2015]. The consumption coefficient for ammonia for the production of urea is taken as an average for all the above technologies (0.580 tons of 100% NH ₃ ). Natural gas consumption for technologies with full liquid recycling includes only the consumption for ammonia production (711 nm ³ ), and for technologies stripping in a current of СО ₂ (133.9 nm ³ ), auto-stripping (in a current of NH ₃ ) (176.2 nm ³⁾ ) and Tecnimont (192.9 nm ³ ), the consumption of natural gas also includes the production of heating steam per ton of urea produced. Nevertheless, the consumption of natural gas is taken as an average for all the above processes.

Thus, to obtain 1 ton of ammonium nitrate, 544 nm ^{3 of} natural gas is required, for 1 ton of carbamide - 795 nm ³ .

Let's recalculate the amount of fertilizers produced from 1000 nm ^{3 of} natural gas. Then from 1000 nm ^{3 of} natural gas we get 1.8 tons of ammonium nitrate, 1.3 tons of carbamide.

We pass to the second block - crop production (see Table 1). Corn was chosen as an example of an energy crop due to its ability to produce high yields. For the planned yield of green mass of corn - 55 t / ha, the fertilizer rate N ₁₂₀ P ₁₂₀ K ₁₄₀ was chosen, where one of the fertilizers under consideration will be used as nitrogen fertilizer. Usually, in real field conditions, a complex of organic and mineral fertilizers is used, but for simplicity of data presentation, one nitrogen-containing mineral fertilizer was chosen to provide plants with nitrogen.

The amount of fertilizer for corn is calculated using the following formula:

where H is the rate of mineral fertilizers, kg per 1 ha; n is the norm of the active substance, kg per 1 ha (120 kg N); d is the content of the active substance in this fertilizer,% (for ammonium nitrate - 34.5% N, for urea - 46.2% N).

Thus, in order to obtain a corn crop of 55 c / ha of green mass, it is necessary to apply 348 kg or 0.348 tons of ammonium nitrate, 260 kg or 0.260 tons of carbamide per hectare of arable land.

Since we have a certain amount of fertilizer (out of 1000 nm ^{3 of} natural gas), it is possible to calculate how many hectares of arable land will be fertilized with the selected nitrogen-containing mineral fertilizer. For ammonium nitrate - 5.2 hectares, for carbamide - 5 hectares.

In turn, from the above data, you can calculate how many tons of grain and green mass of corn will be obtained.

The average grain yield of corn is 5 t / ha, then the amount of grain when using ammonium nitrate will be 26 tons, urea - 25 tons. Considering that about 6.5% of the grain yield will be losses in the process of harvesting, transportation and processing by corn harvesters and cob-cleaning lines and about 4.5% of grain is substandard grain, 23.1 tons of corn grain remain for traditional sale when fertilized with ammonium nitrate, 22.3 tons - for urea. The average price for corn as of 2017 - in the central federal district was 8400 rubles / t, i.e. more than 194 thousand rubles. additional income when using ammonium nitrate, more than 187 thousand rubles. - urea.

After the corn is harvested, agricultural waste (the non-cereal part of the crop) remains in the fields: stalks, leaves, cobs and cobs, which must be sent to the hydrolysis plant. Their quantity when processing the soil with ammonium nitrate will be 286 tons, for urea - 275 tons. Part of the green mass of corn must be left (plowed into the soil) to maintain the balance of soil humus. With re-cultivation of corn and traditional processing technology, the amount of green mass left is about 8.5 t / ha. You should also take into account the loss of biomass during technological operations for its harvesting (harvesting and transportation), which should not exceed 3% of the yield. Thus, 233.22 tons of green mass are sent to a further stage of hydrolysis to obtain bioethanol when the soil is treated with ammonium nitrate, 224.25 tons - with urea. Also, 1.170 tons of substandard grain is sent to the hydrolysis plant using ammonium nitrate, 1.125 tons - urea.

Table 1 shows the average consumption of raw materials for the production of 1 ton of fertilizer, the amount of fertilizer from 1000 nm ^{3 of} natural gas as a feedstock, as well as the number of hectares treated with this amount of fertilizer and the resulting mass of grain and non-food waste of corn.

In the third block, the hydrolysis of green mass of corn and substandard grain was carried out. According to the Russian Biofuel Association, the theoretical yield of bioethanol from a ton of dry corn stalks is 427 liters or, assuming the density of alcohol is 789.3 kg / m ³ , the mass of bioethanol obtained is 0.337 tons, and from dry corn, the output of bioethanol is 470 liters or 0.371 tons. ...

Let us determine the mass of dry non-cereal parts of corn, for this we take the moisture content of the stems and leaves of 33%, the moisture content of the rods - 19%, the moisture content of the wrapper 24% Knowing the ratio of the non-cereal parts of the corn crop in the dry aboveground mass: stems - 40%, leaves - 8%, rods - 6%, cob - 6% of the whole plant mass, as well as the yield of grain and green mass of corn (256.32 t for ammonium nitrate, 246.55 tons for carbamide), we can calculate the mass of non-cereal parts of the corn crop, and then the mass of dry non-cereal parts of corn (see Table 2).

Thus, the total mass of dry non-grain parts of corn is 106.6 tons for ammonium nitrate, and 102.5 tons for carbamide.

In accordance with GOST 13634-90, the moisture content of corn grain should not exceed 15%, therefore, grain with higher moisture content belongs to substandard grain. Let's take the moisture content of substandard grain 16%, then the mass of dry substandard grain for ammonium nitrate is 0.983 t, for urea - 0.945 t.

If we assume that the theoretical yield of bioethanol from one ton of each non-cereal part of the green mass of corn is the same, i.e. 427 liters (or 0.337 tons), and from substandard grain it is equal to 470 liters or (0.371 tons), then the theoretical yield of bioethanol from 106.6 tons of dry green mass will be 35.9 tons, and from 102.5 tons - 34.5 tons The theoretical yield of bioethanol from 0.983 tons of substandard grain will be 0.36 tons, and from 0.945 tons - 0.35 tons. Then the total theoretical output of bioethanol when using ammonium nitrate is 36.26 tons, and when using urea - 34.85 tons ( see Table 3).

In the fourth block of the scheme, organic-mineral fertilizers and related products (lawns, enriched garden soil, flower soil) are obtained from the waste of nitrogen-containing mineral fertilizers, plant growing and hydrolysis production.

In the fifth block of the scheme, the rectification separation of the liquid hydrolysis hydrocarbon-containing solution and the purification of the mixture were carried out. Further, the hydrocarbon-containing feedstock in the vapor phase, after additional purification, to exclude withdrawals and inappropriate use, is fed for catalytic processing on high-silicon zeolites into gaseous and liquid hydrocarbon products with a composition close to natural oil and gas products. After analyzing a number of scientific sources on this topic [Isa Yusuf. Conversion of ethanol on zeolite catalysts / Abstract diss. for a job. uch. Art. Cand. tech. sciences. - M., 2009 .-- 24 p; Pilipenko A.Yu. ethanol conversion on the catalyst Zr-ZSM-5 / Bulletin of the Saratov University. New series. Chemistry series. Biology. Ecology, 2014, T. 14, No. 3, p. 25-30; Chudakova M.V. Conversion of ethanol and cellulose into hydrocarbon fuel components in the presence of nanoscale bimetallic catalysts / Abstract of a thesis for a dissertation. uch. senior cand. chem. sciences. - M., 2012. - 27 p.], It was assumed that during the conversion of gaseous products 10% is formed, liquid hydrocarbons - 40%, water - 50%, the degree of conversion of bioethanol into hydrocarbon products is 85%. Then the amount of reacted bioethanol when using ammonium nitrate is 30.82 tons, and when using urea - 29.62 tons. From 30.82 tons of bioethanol, 3.08 tons of gaseous products, 12.33 tons of liquid hydrocarbons, 15.41 tons of water are obtained From 29.62 tons of bioethanol, 2.96 tons of gaseous products, 11.85 tons of liquid hydrocarbons, 14.81 tons of water are obtained (see Table 4).

A part of the obtained gaseous products is processed into natural gas and, in order to expand the production, about 1.5 share is recycled to the first unit for the production of nitrogen-containing mineral fertilizers. Recycling more natural gas is needed to extend the production cycle. Since for the production of nitrogen-containing mineral fertilizers 0.73 tons of natural gas (mass of 1000 nm ^{3 of} natural gas) were consumed, then 1.095 tons of natural gas must be returned to the initial stage of the process. The remaining hydrocarbon products are sent for processing into final products required by the customer (commercial gasoline, diesel fuel, ethylene, divinyl, biohydrogen, etc.).

As a result, by means of the presented closed extended scheme it is possible to obtain more than ten tons of hydrocarbon containing products from one cubic meter of feedstock (natural gas). In this case, the amount of initial substances is specified using parametric profit optimization, the regulating parameter of which is present in each component of the cycle, since the local optimum in which the ecological systems and nodes of the technological scheme operate does not provide, as is known, the global optimum of the entire technological scheme as a whole. Thus, the presented scheme is flexible and easily adaptable to specific initial conditions and customer requirements.

The implementation of the claimed method allows for an environmentally friendly and economically viable scheme to obtain motor fuel, which can become an alternative to fossil fuels, thereby significantly reducing emissions of pollutants and the depletion of world hydrocarbon reserves.

Claims (4)

1. A method for the production of hydrocarbon products from bioethanol obtained from plant biomass, characterized in that it includes the following stages: from the first intermediate - natural gas, the second intermediate - nitrogen-containing mineral fertilizers are obtained, which are applied to the soil during the growing season of agricultural crops to obtain a crop of crop products - the third intermediate product, while the conditioned part of the crop is processed or sold to the consumer, and the substandard part and green mass are sent to the stage of biochemical processing - hydrolysis, where, after rectification separation and purification, a hydrocarbon component is obtained in the form of an ethanol-containing mixture in the vapor phase - the fourth intermediate product, as well as waste production; further, the specified ethanol-containing mixture in the vapor phase, after additional purification, is sent for catalytic processing into gaseous and liquid hydrocarbon products with a composition close to natural oil and gas products - the fifth intermediate product, of which part of the gaseous products is processed into natural gas and returned to the stage of obtaining nitrogen-containing mineral fertilizers, in a larger amount than was used in the first stage, and the rest of these gaseous products and liquid hydrocarbon products are sold as the final product. 2. The method according to claim 1, characterized in that the obtained gaseous and liquid hydrocarbon products are "artificial" gas or oil, similar in their properties to natural oil and gas products. 3. The method according to claim 1, characterized in that the final product is commercial gasoline or diesel fuel. 4. The method according to claim 1, characterized in that the production wastes from the hydrolysis stage are used as organomineral fertilizers or additives to animal feed.

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