RU2649629C1 - Method of synthetic oil production from natural or associated petroleum gas (variants) - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: present invention relates to embodiments of the synthetic petroleum production process from natural or associated petroleum gas. One embodiment of the method includes a stage of oxygenates synthesizing from the initial synthesis gas obtained from said feedstock in the presence of a metal oxide catalyst, with production of a mixture comprising oxygenates, a stage of hydrocarbons producing from said mixture in the presence of a zeolite catalyst, a stage of the hydrocarbons separating into a liquid organic phase, which is withdrawn as a product, gas phase and aqueous condensate of the hydrocarbons production stage, and a stage of the gas phase portion returning to the oxygenate synthesis reactor as a circulating gas. At that, the circulation frequency is 3-5, metal catalyst is a catalyst obtained by an industrial copper-zinc-aluminum catalyst MegaMax-507 and active alumina tableting taken in a weight ratio of (1-2) / 1, with a colloidal graphite in an amount of 1.0% by weight of the catalyst, and as the zeolite catalyst is a catalyst based on a decaffeinated zeolite type ZSM-5 modified with zinc and a metal selected from the family of platinum subgroup VIIIB, with composition, wt%: Na₂O – 0.09, said metal is 0.1 - 0.5, Fe₂O₃ – 0.5-1.0, ZnO – 2.0-5.0, Al₂O₃ – 25.0, SiO₂ - the rest, prior to the stage of hydrocarbons producing from the oxygenates containing mixture, preliminarily recovering the aqueous condensate of the oxygenate synthesis stage, which is sent for mixing with the aqueous condensate of the hydrocarbon production stage, the resulting mixture of condensates is sent to a rectification column, and the rectification column distillate with a methanol content of not less than 89.0% by weight is sent to the oxygenates synthesis reactor.

EFFECT: proposed method variants allow to produce synthetic oil with a low content of aromatic compounds while maintaining selectivity.

2 cl, 2 dwg, 2 tbl, 8 ex

Description

The invention relates to petrochemistry and more specifically to a method for producing synthetic oil by catalytic conversion of oxygenates (dimethyl ether (DME) and methanol) obtained from natural or associated gas through a mixture of H ₂ , CO and CO ₂ (synthesis gas). The invention can be used to obtain synthetic oil with a low content of aromatic compounds, similar in composition to gas condensate and suitable, depending on various tasks, for injection into the pipeline to increase the profitability and productivity of the oil well.

The volume of associated petroleum gas (APG) produced in Russia in 2011 amounted to 67.8 billion m ³ (see A.G. Korzhubaev, D.A. Lamert, L.V. Eder. Problems and prospects of effective the use of associated petroleum gas in Russia // Drilling and Oil. 04/2012), in 2013 - 74.4 billion m ³ (see, Report of the head of the gas industry monitoring group of the Central Control Department of the Fuel and Energy Complex A. Artamonova. // 4th International CREON Energy conference “Associated Petroleum Gas 2013. Moscow, March 26, 2013, URL: <http://www.creonenergy.ru/consulting/detailConf.php?ID=109836>. date 11.16.2016).

The rational use of associated gas in Russia is realized at 76%, of which about 45% of the total production is supplied to the gas transmission network and sent to gas processing plants to produce dry gas (LOG), a wide fraction of light hydrocarbons (BFLH), liquefied gases (LHG) and stable gasoline (GBS), and about 31% is used for the own needs of oil companies - re-injection of APG into the oil reservoir to increase oil recovery and the production of electric energy to ensure energy autonomy of the field.

Irrational use of APG is 24%: in 2012-2014, 15.8-17.1 billion m ^{3 of} APG was sent for combustion (see the indicated Report), which amounts to about $ 5 billion in monetary equivalent of financial losses ( Knizhnikov A.Yu., Pusenkova NN Problems and prospects for the use of associated petroleum gas in Russia // Working materials of the annual review of the problem within the framework of the IMEMO RAS and WWF Russia project “Ecology and Energy. International Context. 2015. Issue 1) . And every year the volumes of improper use of associated gas are increasing due to the discovery of new fields in areas with poorly developed infrastructure for processing and transportation.

The problem of APG utilization has not only an economic, but also an environmental aspect, since emissions from APG combustion are soot, CO ₂ , and sulfur and nitrogen oxides.

The solution to the problem of APG processing in the absence of developed infrastructure, i.e. in the fields, there may be an option of processing APG into synthetic oil suitable for transportation along the pipeline along with oil.

The traditional scheme of processing gas (natural, associated, bio-) into liquid hydrocarbons includes the stages:

synthesis gas production

Obtaining oxygenates in two stages:

synthesis gas → methanol → DME,

or one stage:

synthesis gas → methanol + DME + water,

and hydrocarbon synthesis.

All known technologies include gas phase recycling, which is organized separately at the oxygenate synthesis stage and separately at the gasoline synthesis stage (Exxon Mobil (USA), Chemieanlagenbau Chemnitz and Freiberg Mining Academy (Germany)), or several stages are combined into a single circulation circuit (Primus Green Energy (USA), INHS RAS (RF)). It should be noted that STK Zeosit and Haldor Topsoe have patents for the implementation of both the first and second options for organizing recycling.

A known method of producing gasoline company Haldor Topsoe according to the patent of the Russian Federation No. 2448147 C2, publ. 04/20/2012, according to which the synthesis of hydrocarbon components of gasoline from synthesis gas is carried out through oxygenate-containing raw materials, including methanol and / or DME and a mixture containing up to 1.0% wt. other oxygenates (C ₂ -C ₆ alcohols, ethers of higher alcohols C ₃₊ ). The synthesis of oxygenates is carried out at a temperature of 200-350 ° C, a pressure of 25-150 bar on a catalyst containing Al ₂ O ₃ , aluminosilicate and / or zeolite, as well as Cu and / or ZnO. After the stage of synthesis of oxygenates, the stream is cooled, condensed, and liquid and gas phases are isolated. The gas phase is used as bypass in the oxygenate synthesis reactor. The liquid phase is directed to the synthesis of gasoline at a temperature of 300-450 ° C, a pressure of 25-150 bar on a HZSM-5 zeolite catalyst. After the stage of hydrocarbon synthesis, the stream is cooled, condensed, and the liquid (aqueous and organic) and gas phases are isolated. The gas phase is directed to mixing with the original synthesis gas, the entire stream is purified from CO ₂ and fed to the stage of synthesis of oxygenates or to the stage of synthesis of gasoline. Thus, we can say that the two stages are combined by a single circulation circuit.

In Haldor Topse application WO 2016/116612 A1 dated 01/22/2015, gasoline is synthesized at a temperature of 370-420 ° C, a pressure of 20 bar using HZSM-5 zeolite modified with metals as a catalyst (Zn, Ga, In, Mo, Ag, P, Ge, Sn, Pd, Pt). According to the presented examples, the content of aromatic compounds in the product is 35-55% wt., Durene - 1.5-8.5% wt.

A known method of producing transport fuel, including gasoline, from the synthesis gas of the company Primus Green Energy according to the patent of the Russian Federation No. 2574390 C2, publ. 02/10/2016, according to which the production of fuel is carried out in four successive catalytic reactors, including a reactor for the synthesis of methanol, DME, hydrocarbons and the conversion of heavy gasoline, with intermediate heat transfer between the reactors, but without separation of the products between them, at a pressure of 50-100 atm. After the 4th reactor, the contact gas is cooled and condensed. Gases that did not react in the 4th reactor are recycled to the first reactor. Water condensate and liquid hydrocarbons are removed from the circuit. The resulting product contains 30-40% wt. iso- and n-paraffins C ₅ -C ₈ , 15-25% wt. cycloparaffins C ₆ -C ₈ , 2-5% wt. toluene, 6-10% wt. xylene, 10-15% wt. trimethylbenzenes, 15-20% wt. tetra- and to a higher degree substituted benzene, including durene.

Methanol synthesis in the first reactor is carried out using a CuO / ZnO / Al ₂ O ₃ catalyst at a temperature of 220-260 ° C, DME synthesis in a second reactor using γ-Al ₂ O ₃ at a temperature of 400-420 ° C, hydrocarbon synthesis on ZSM-5 zeolite at a temperature of 343-420 ° C, heavy gasoline conversion - on a metal oxide catalyst reduced in the presence of H ₂ (or a mixture of H ₂ / CO) containing metal oxides of IX, X, VI groups (Ni, Co, Mo) , on an aluminum oxide carrier at a temperature of 150-180 ° C.

The invention is demonstrated by the results of tests on a plant with a capacity of 5-10 g / h for liquid fuel, consisting of 4 Berty reactors connected in series, united by one circulation loop. At the same time, there are no diffusion restrictions in the Berty reactor due to the presence of internal circulation, and strictly speaking, the presented results cannot be qualified to scale to a large plant power.

A known method of producing hydrocarbons from carbon monoxide and hydrogen, ZAO "STK" Zeosit ", RF Patent No. 2284312 C1, publ. 09/27/2006, according to which the conversion of synthesis gas to C ₅₊ hydrocarbons is carried out in one stage, consisting of two reaction zones: a bifunctional catalyst based on zeolite ZSM-5 or ZSM-11 and a metal oxide component (ZnO-Cr) is used in the first reaction zone ₂ O ₃ -W ₂ O ₅ ), in the second reaction zone a multifunctional acid catalyst based on ZSM-5 or ZSM-11 is used. The process is carried out without cooling, condensation and separation of products between two zones in a single circulation circuit with a circulation ratio of 60-400, a pressure of 40-100 atm and a temperature in the reaction zones T ₁ = 340-420 ° C and T ₂ = 340-460 ° C. The selectivity of gasoline formation is 70-82% wt., And the resulting product, depending on the composition of the catalyst used, may contain from 20-25 to 40-50% wt. aromatic compounds.

The disadvantage of all these inventions is the high content of aromatic compounds in the final product, and the associated problems of transporting liquid hydrocarbons through pipelines.

Closest to the claimed is a method for producing synthetic oil - a mixture of hydrocarbons according to the patent of the Russian Federation No. 2442767, С07С 1/04, 02/20/2012. According to this method, the initial synthesis gas obtained from any raw material, including associated petroleum gases, is mixed with circulating gas and fed to the first reactor, in which the synthesis of oxygenates (DME and methanol) is carried out on a combined metal oxide catalyst at a pressure of 5-10 MPa and in the temperature range 220-300 ° C. Then the gas-vapor mixture from the oxygenate synthesis reactor without their intermediate separation from the unconverted components of the synthesis gas enters the second reactor, where, in the presence of a pentasil type zeolite catalyst containing zinc oxide and palladium, at the same pressure as in the oxygenate synthesis reactor, and a temperature of 340-360 ° C carry out the synthesis of hydrocarbons. The contact mixture from the reactor enters the separator, where it is separated into an aqueous, liquid organic and gas phase. The gas phase containing unreacted components of the synthesis gas and light hydrocarbon gases C ₁ -C ₄ is divided into two streams. The main part of the flow enters the inlet of the circulation compressor and returns to the oxygenate synthesis reactor. The second part of the stream (purge gas) is discharged into the atmosphere or is used as fuel gas for technical needs. This method allows to obtain high-quality and environmentally friendly high-octane gasoline with an octane rating of at least 90 points according to the research method that meets international standards, with high selectivity - the yield of C ₅₊ hydrocarbons is 67.2-79.3% wt.

According to this patent, at the stage of synthesis of oxygenates, a copper-zinc-chromium catalyst of the composition is used,% wt .: CuO - 23.25; ZnO 23.25; Cr ₂ O ₃ - 16.6; Al ₂ O ₃ - 36.9, developed and patented by the Institute of Chemical Economy of the Russian Academy of Sciences (RF Patent №2218988, 2003). At the stage of synthesis of high-octane gasoline, a catalyst based on zeolites of the pentasil type with SiO ₂ / Al ₂ O ₃ = 25-100 composition, wt.%: ZnO - 0.1-3.0; Pd 0.1-1.0; zeolite - 50-70; the rest is a binder, developed and patented by the Institute of Chemical Economy of the Russian Academy of Sciences (RF Patent No. 2248341, 2005). The disadvantages of the presented method are:

the high content of aromatic compounds in the resulting mixture is 16.1-30.0 wt.%, which prevents the use of the resulting mixture of hydrocarbons for injection into the pipeline;

the use at the stage of synthesis of oxygenates of a catalyst containing toxic chromium compounds, which is currently discontinued due to increased environmental requirements for the synthesis and disposal of catalysts. This prevents the application of the known method in industry.

In addition, according to the examples presented in the patent, in the case of using the initial synthesis gas with a low concentration of CO, it is possible to maintain high productivity only due to the high multiplicity of circulation - 10 vol./vol., Which increases the energy consumption for the production of finished products.

As a catalyst of the first stage, a catalyst prepared on the basis of a copper-zinc-aluminum industrial methanol synthesis catalyst MegaMax-507 and industrial active alumina taken in various proportions (see table 1) can be used, which in terms of its performance (CO conversion, selectivity for the formation of DME and methanol) is superior to the Cu-Zn-Cr catalyst.

However, the authors found that the use of a MegaMax-507 / Al ₂ O ₃ mixture in a different ratio at the stage of oxygenate synthesis in conjunction with a zeolite catalyst for gasoline synthesis (НХС-1 composition,% wt .: ZnO - 0.1-3.0; Pd - 0.1-1.0; zeolite - 50-70; the rest is a binder) reduces the selectivity of the formation of hydrocarbons. This is due to the high hydrogenating / hydrocracking activity of palladium, one of the main components of the synthetic oil synthesis catalyst, under conditions of low CO concentration in the circulating gas and low zeolite catalyst activity in the DME conversion, which leads to carbon losses in the form of methanol in the aqueous phase after the production stage synthetic oil.

The use of a new zeolite catalyst based on decationized zeolite of the ZSM-5 type, modified with zinc and a metal selected from the platinum family of subgroup VIIIB, developed at the Institute of Chemical Economy of the Russian Academy of Sciences - NHS-2 together with MegaMax-507 / Al ₂ O ₃ ((1-2) / 1 / graphite), allows to increase the selectivity of the formation of synthetic oil with a high ratio of circulation. However, a decrease in the multiplicity of circulation leads to an increase in the content of aromatic compounds, and, in particular, durene in the composition of synthetic oil.

The objective of the proposed technical solution is to develop a comprehensive industrial process for the processing of associated petroleum gas into synthetic oil, which, when used in an industrial environment, provides a low content of aromatic compounds in the resulting product, maintaining productivity at a low circulation rate and utilizing methanol, which reduces the consumption of the initial synthesis gas .

The task according to the first embodiment of the invention is solved in that in a method for producing synthetic oil from natural or associated petroleum gas, comprising the step of synthesizing oxygenates from an initial synthesis gas obtained by known methods from said raw materials, in the presence of a metal oxide catalyst, to obtain a mixture containing oxygenates, a step for producing hydrocarbons from said mixture in the presence of a zeolite catalyst, a step for separating hydrocarbons into a liquid organic phase, which It is a product, gas phase and water condensate of the hydrocarbon production stage and the stage of returning part of the gas phase to the oxygenate synthesis reactor as a circulating gas, the multiplicity of circulation is 3-5, the catalyst obtained by tabletting the industrial copper-zinc catalyst MegaMax-507 and active aluminum oxide, taken in the ratio (1-2) / 1, with colloidal graphite in an amount of 1.0% by weight of the catalyst, as a zeolite catalyst, a catalyst based decationized zeolite type ZSM-5, modified with zinc and a metal selected from the platinum family of subgroup VIIIB, composition,% wt .: Na ₂ O - 0.09, the metal 0.1-0.5, Fe ₂ O ₃ - 0, 5-1.0%, ZnO - 2.0-5.0, Al ₂ O ₃ - 25.0, SiO ₂ - the rest, before the stage of hydrocarbon production from the mixture containing oxygenates, the water condensate of the oxygenate synthesis stage is preliminarily isolated, which sent for mixing with the aqueous condensate of the hydrocarbon production stage, the resulting mixture of condensates is sent to a distillation column, and the distillate of the distillation column with the content of methanol is not less than 89.0% wt. sent to the oxygenate synthesis reactor.

According to a second embodiment of the invention, from a distillate of a distillation column with a methanol content of at least 89.0% wt. by decomposition, syngas components are obtained which are mixed with the feed syngas.

As a catalyst for the synthesis of oxygenates, it is proposed to use a catalyst consisting of MegaMax-507 industrial copper-zinc catalyst and industrial active alumina, taken in a mass ratio of (1-2) / 1, and colloidal graphite in an amount of 1.0% by weight of the catalyst.

It is proposed to use the catalyst NHX-2, a zeolite catalyst based on a decationized zeolite of the ZSM-5 type, modified with zinc and a metal selected from the platinum family of subgroup VIIIB, as a catalyst,% wt .: Na ₂ O - 0.09, said metal is 0.1-0.5, Fe ₂ O ₃ is 0.5-1.0, ZnO is 2.0-5.0, Al ₂ O ₃ is 25.0, SiO ₂ is the rest. The metals of the platinum family of subgroup VIIIB include platinum, ruthenium, rhodium, palladium, osmium, iridium. The separation of water condensate after the oxygenate synthesis reactor leads to a decrease in the content of aromatic compounds in the product while maintaining the selectivity of hydrocarbon formation.

The synthesis gas can be obtained by known methods (for example, steam, oxygen or carbon dioxide conversion) from associated petroleum gas or from natural gas, the main component of which is methane.

Technological methods for the implementation of the technology on a pilot scale — the return of methanol to the oxygenate synthesis reactor and the decomposition of methanol to synthesis gas — increase the plant's productivity and solve the problem of wastewater disposal.

A catalyst for the synthesis of oxygenates is obtained by tabletting a mixture consisting of MegaMax-507, which is produced according to TU U 24.6-31337612-010: 2009, and active alumina, taken in amounts that provide a ratio of MegaMax-507 and active alumina equal to (1-2) /one. Active alumina complies with GOST 8136-85 and is γ-Al ₂ O ₃ . For better tableting, 1.0% wt. graphite of colloidal grade S-1 (TU 113-08-48-63-90).

The technical result from the use of the proposed technical solution is to obtain synthetic oil with a low content of aromatic compounds, which is an analogue of gas condensate in its composition, while maintaining the selectivity of its formation under the conditions of using the initial synthesis gas with a high concentration of hydrogen and a low circulation ratio (not more than 5) and increased installation performance. An additional effect is the use of a non-toxic catalyst in the first stage of oxygenation.

In FIG. 1 shows a process diagram of the prototype.

In FIG. 2 is a flow diagram of a process of the invention, showing both embodiments of the invention.

In the diagrams:

Devices:

1 - reactor for the synthesis of oxygenates,

2 - a hydrocarbon production reactor,

3 - three-phase separator,

4 - circulation compressor,

5 - two-phase separator,

6 - distillation column,

7 - decomposition reactor,

8 - discharge compressor.

Streams:

9 - source synthesis gas,

10 - circulating gas

11 - contact gas of the 1st stage,

12 - water condensate of the 2nd stage,

13 - synthetic oil,

14 - blowing,

15 - water condensate of the 1st stage,

16 - gas phase,

17 - water

18 and 19 — methanol — distillate of a distillation column with a methanol content of at least 89.0% wt. (according to the first and second embodiments of the invention, respectively).

20 - contact gas of the 2nd stage.

In the event that methanol is sent by stream 18 to the oxygenate synthesis reactor 1, the first embodiment of the invention is implemented. In the event that methanol is instead directed by stream 19 to a decomposition reactor 7, then to a heating compressor 8 and mixed with the original synthesis gas, a second embodiment of the invention is implemented.

The invention is illustrated by the following examples, confirming the effectiveness of the proposed method for producing synthetic oil.

Example 1 (prototype).

The process is carried out according to the circuit depicted in FIG. 1. The original synthesis gas (stream 9) composition,% vol .: H ₂ - 59; СО - 33; CO ₂ - 2; N ₂ - 5, obtained from associated petroleum gas, is fed to a mixture with circulating gas (stream 10). Next, the mixture enters the first reactor — the oxygenate synthesis reactor (1), in which, on a combined metal oxide catalyst,% wt.: CuO — 23.25; ZnO 23.25; Cr ₂ O ₃ - 16.6; Al ₂ O ₃ - 36.9 carry out the synthesis of oxygenates (DME and methanol). The pressure in the system is 10.0 MPa. Further, the synthesis of oxygenates is briefly referred to as the 1st stage. Then the gas-vapor mixture from the oxygenate synthesis reactor — stage 1 contact gas (stream 11) —without their intermediate separation from the unconverted components of the synthesis gas, is sent to the second reactor (2) —the hydrocarbon production reactor, where, in the presence of a zeolite catalyst,% wt .: ZnO - 0.1-3.0; Pd 0.1-1.0; zeolite CVM - 50.0-70.0; the binder is the rest, at the same pressure as in the oxygenate synthesis reactor, the synthesis of hydrocarbons is carried out (hereinafter referred to briefly as the 2nd stage). The contact mixture from the reactor (2) (stream 20) enters a three-phase separator (3), where it is separated into an aqueous, liquid organic and gas phase. The aqueous phase is an aqueous condensate after the 2nd stage (stream 12) with a methanol concentration of 5.0% wt. deduced from the process. The main part of the gas phase containing unreacted components of the synthesis gas and light hydrocarbon gases C ₁ -C ₄ is directed to the inlet of the circulation compressor (4) and returned to the oxygenate synthesis reactor (1) as a circulating gas (stream 10). The rest of the gas phase in the form of purge (stream 14) is removed from the process. The liquid organic phase is removed from the three-phase separator (3) as a synthetic oil product (stream 13). The multiplicity of circulation is 10.

Example 2 (prototype).

The process is carried out analogously to example 1 using the composition as a starting synthesis gas,% vol .: H ₂ - 75; СО - 13; CO ₂ - 7; N ₂ - 5. The aqueous condensate after the 2nd stage is removed with a methanol concentration of 23.0% wt.

Example 3

The process is carried out according to the circuit depicted in FIG. 2.

The gas stream consisting of the initial synthesis gas composition,% vol .: H ₂ - 74; СО - 19; CO ₂ - 5; N ₂ - 2 (stream 9), and circulating gas (stream 10), is fed to the oxygenate synthesis reactor (1). The pressure in the system is 9.0 MPa. The gas temperature at the inlet of the oxygenate synthesis reactor is 240 ° C. In it, on a combined metal oxide catalyst composition,% wt .: CuO - 30.2, ZnO - 15.4, Al ₂ O ₃ - 53.4, graphite - 1.0, the synthesis of oxygenates (DME and methanol) is carried out. The catalyst was obtained by tabletting a mixture consisting of MegaMax-507 and active alumina Al ₂ O ₃ , taken in a mass ratio of 1 to 1, with the addition of graphite. Then the gas-vapor mixture from the reactor (1) - the contact gas of the 1st stage (stream 11) - is cooled and separated into a gas phase and an aqueous phase in a two-phase separator (5). The aqueous phase is water condensate after the 1st stage (stream 15) with a methanol concentration of 40.0% wt. sent for mixing with aqueous condensate of the 2nd stage (stream 12). The gas phase (stream 16) is sent to a hydrocarbon production reactor (2), where, in the presence of an NHC-2 zeolite catalyst, composition, wt%: Na ₂ O - 0.09, Pd - 0.5, Fe ₂ O ₃ - 1, 0, ZnO - 2.0, Al ₂ O ₃ - 25.0, SiO ₂ - 71.41 - at the same pressure as in the oxygenate synthesis reactor, synthetic oil is synthesized. The gas temperature at the inlet to the hydrocarbon production reactor is 340 ° C. The contact mixture from the reactor (2) (stream 20) enters the three-phase separator (3), where it is separated into aqueous, liquid organic and gas phases. The main part of the gas phase containing unreacted components of the synthesis gas and light hydrocarbon gases C ₁ -C ₄ is sent to the inlet of the circulation compressor (4) and returned to the reactor (1) as circulating gas (stream 10). The rest of the gas phase in the form of purge (stream 14) is removed from the process. The aqueous phase - water condensate after the 2nd stage (stream 12) in a mixture with water condensate after the 1st stage (stream 15) is sent to a distillation column (6). The distillation of a distillation column with a methanol content of 99.0% wt. (stream 18) is sent to the reactor (1). The separated process water (stream 17) is removed from the process. The liquid organic phase from the three-phase separator (3) is removed as a synthetic oil product (stream 13). The multiplicity of circulation is 5.

Example 4. Carried out analogously to example 3 with the difference that the frequency of circulation is 3.5.

At the stage of the synthesis of synthetic oil, an NHC-2 catalyst of the composition is used, wt%: Na ₂ O - 0.09, Rh - 0.46, Fe ₂ O ₃ - 0.8, ZnO - 3.0, Al ₂ O ₃ - 25.0, SiO ₂ - 70.65.

Example 5. Carried out analogously to example 3 with the difference that they use the original synthesis gas composition,% vol .: H ₂ - 59; СО - 33; CO ₂ - 6; N ₂ - 2.

At the stage of the synthesis of synthetic oil, an NHX-2 catalyst of the composition is used, wt%: Na ₂ O - 0.09, Pt - 0.21, Fe ₂ O ₃ - 0.5, ZnO - 5.0, Al ₂ O ₃ - 25.0, SiO ₂ - 69.2.

Example 6. Carried out analogously to example 3 with the difference that the distillate of the distillation column contains 89.0% wt. methanol.

At the stage of the synthesis of synthetic oil, an NHX-2 catalyst of the composition is used,% wt .: Na ₂ O - 0.09, Pd - 0.21, Fe ₂ O ₃ - 0.7, ZnO - 2.5, Al ₂ O ₃ - 25.0, SiO ₂ - 71.5.

Example 7

The process is carried out according to the circuit depicted in FIG. 2.

Carried out analogously to example 3 with the difference that the distillate allocated in the distillation column (6) with a methanol content of 99.0% wt. (the rest is water) is sent not to the oxygenate synthesis reactor (1), but to the decomposition reactor (7) as stream 19 to produce synthesis gas components, where the distillate is decomposed on an industrial palladium-carbon catalyst on coal at a temperature of 360 ° C and a pressure of 0.2 MPa. The components of the synthesis gas are compressed using an injection compressor (8) and sent to mixing with the original synthesis gas (stream 9).

At the stage of the synthesis of synthetic oil, an NHX-2 catalyst of the composition is used, wt%: Na ₂ O - 0.09, Rh - 0.11, Fe ₂ O ₃ - 0.7, ZnO - 2.5, Al ₂ O ₃ - 25.0, SiO ₂ 71.6.

Example 8

Carried out analogously to example 7 with the difference that the distillate contains 89.0% wt. methanol.

At the stage of the synthesis of synthetic oil, an NHX-2 catalyst of the composition is used, wt%: Na ₂ O - 0.09, Pt - 0.11, Fe ₂ O ₃ - 1.0, ZnO - 3.5, Al ₂ O ₃ - 25.0, SiO ₂ - 70.3.

The process conditions and results are given in table. 2.

The implementation of the method according to the invention when used in an industrial environment provides a low content of aromatic compounds in synthetic oil, maintaining performance at low circulation rates, utilizing methanol and reducing the consumption of the original synthesis gas by 10-12% vol. when used in the first stage of a non-toxic catalyst.

Claims (2)

1. A method of producing synthetic oil from natural or associated petroleum gas, comprising a step for synthesizing oxygenates from a feed synthesis gas obtained from said feedstock in the presence of a metal oxide catalyst, to obtain a mixture containing oxygenates, a step for producing hydrocarbons from said mixture in the presence of a zeolite catalyst , a stage for separating hydrocarbons into a liquid organic phase, which is discharged as a product, a gas phase and an aqueous condensate of a hydrocarbon production stage, and a part returning stage the gas phase in the reactor for the synthesis of oxygenates as a circulating gas, characterized in that the circulation ratio is 3-5, as the metal oxide catalyst used is a catalyst obtained by tabletting an industrial copper-zinc catalyst MegaMax-507 and active alumina taken in a mass ratio (1-2) / 1, with colloidal graphite in an amount of 1.0% by weight of the catalyst, as a zeolite catalyst, a catalyst based on decationized zeolite type ZSM-5, modified with zinc and metal, in selected from the platinum family of subgroup VIIIB, composition, wt.%: Na ₂ O - 0.09, said metal 0.1-0.5, Fe ₂ O ₃ - 0.5-1.0, ZnO - 2.0- 5.0, Al ₂ O ₃ - 25.0, SiO ₂ - the rest, before the stage of hydrocarbon production from the mixture containing oxygenates, the water condensate of the oxygenate synthesis stage is preliminarily separated, which is sent to the hydrocarbon production stage for mixing with the water condensate, the resulting mixture of condensates sent to the distillation column, and the distillate of the distillation column with a methanol content of at least 89.0 wt.% sent to the oxygenate synthesis reactor at. 2. A method of producing synthetic oil from natural or associated petroleum gas, comprising a step for synthesizing oxygenates from a starting synthesis gas obtained from said feedstock in the presence of a metal oxide catalyst, to obtain a mixture containing oxygenates, a step for producing hydrocarbons from said mixture in the presence of a zeolite catalyst , a stage for separating hydrocarbons into a liquid organic phase, which is discharged as a product, a gas phase and an aqueous condensate of a hydrocarbon production stage, and a part returning stage the gas phase in the reactor for the synthesis of oxygenates as a circulating gas, characterized in that the circulation ratio is 3-5, as the metal oxide catalyst used is a catalyst obtained by tabletting an industrial copper-zinc catalyst MegaMax-507 and active alumina taken in a mass ratio (1-2) / 1, with colloidal graphite in an amount of 1.0% by weight of the catalyst, as a zeolite catalyst, a catalyst based on decationized zeolite type ZSM-5, modified with zinc and metal, in selected from the platinum family of subgroup VIIIB, composition, wt.%: Na ₂ O - 0.09, said metal 0.1-0.5, Fe ₂ O ₃ - 0.5-1.0, ZnO - 2.0- 5.0, Al ₂ O ₃ - 25.0, SiO ₂ - the rest, before the stage of hydrocarbon production from the mixture containing oxygenates, the water condensate of the oxygenate synthesis stage is preliminarily separated, which is sent to the hydrocarbon production stage for mixing with the water condensate, the resulting mixture of condensates sent to the distillation column, and from the distillate of the distillation column with a methanol content of at least 89.0 wt.% by decomposition receive component s synthesis gas, which are mixed with the original synthesis gas.

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