A method of producing hydrocarbons from carbon oxides and hydrogen

 

Usage: petrochemistry. The inventive spending contacting the synthesis gas with a catalytic composition consisting of a mixture of iron catalyst for Fischer-Tropsch synthesis in oxidized or reduced form, promoted by oxides of aluminum, silicon, magnesium, potassium and calcium, and acid component of the crystalline aluminosilicate or silicoaluminate. Use the circulation gas stream after reactor volume ratio of the number of circulating gas to the raw synthesis gas, equal 1-1000, and the process is performed at a pressure of 10-100 ATM, a temperature of 220-400oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH the source sites gas equal to 1-3, and volumetric content of CO2in the gas stream at the inlet to the reactor is from 0.01 to 40%. Effect: increase the selectivity and productivity of the catalyst in the liquid hydrocarbon. 6 C.p. f-crystals, 1 table.

The invention relates to organic chemistry, namely to the petrochemical industry and, in particular, to a method for producing hydrocarbons from a mixture of CO, H2and CO2(hereinafter referred to as synthesis gas). As the catalyst used consumability (zeolites) or silicoaluminate different patterns. The resulting hydrocarbon fraction can be applied for practical purposes as gasoline and diesel fuel with a low content of benzene and aromatic hydrocarbons and, consequently, high content of aliphatic hydrocarbons out-buildings, as well as raw materials for obtaining basic components of motor oils.

A method of obtaining C5+hydrocarbons from the gas containing H2and, by contacting the gas at a temperature of 180-250oC, a pressure of from 15 to 50 ATM and the volume ratio of N2/CO is 1.1 to 1.8, with a catalyst containing cobalt and zirconium on the media selected from a silicate or oxide of silicon, aluminum, titanium (patent 1833355 RF, CL C 07 C 1/04, 1993, [1]).

Also known is a method of obtaining cobalt-zirconium catalyst on Al2AboutCfor the synthesis of C5+hydrocarbons from the gas containing H2and applied at a temperature of 150-350oWith the pressure of 10-70 MPa and the volume ratio of N2/FROM 1.0 to 2.3 (patent 1836146 RF, CL 01 J 37/04, 21/04, 23/74, 1993, [2]).

According to these methods, as a result of the transformation mixture of N2and WITH a cobalt-zirconium catalysts are obtained With5+hydrocarbons with high selectionstyle the cost of the catalyst and a low content of ISO-paraffins in the reaction products.

Closest to the invention in its technical essence is a method of producing hydrocarbons from synthesis gas with a molar ratio of N2/SD= 1,6, diluted with nitrogen to 50 vol.%, when contacting at a pressure of 30 ATM and temperatures 230-320oWith binary catalytic systems based catalysts for Fischer-Tropsch synthesis (SFT) and zeolite ZSM-5 (Vitova L. A., Kluger, A., Bogolepov E. I. and others, Petrochemicals, 2001, T. 41, 3, S. 201-208, [3]).

According to the prototype of the liquid products of the conversion of synthesis gas are gasoline fraction (5-C10hydrocarbons), diesel fraction (10-C20hydrocarbons), paraffin waxes With21+and the reaction water containing oxygen-containing compounds. In this work (prototype) there are a number of disadvantages: 1) high metanoobrazovanie from 17 to 40 wt.% from the amount of hydrocarbons; 2) low selectivity and productivity of the catalyst liquid (C5+) hydrocarbons 37-50 wt.% and 34-98 g/l cat./h, respectively; 3) low yield of liquid hydrocarbons filed with the synthesis gas, not exceeding 70 g/nm3CO+H2; 4) low degree of useful use "carbon" source of synthesis gas, i.e., the number passed "whereeveryone WITH, formed side in gaseous hydrocarbons and alcohols, as well as pass in CO2that are harmful to the environment of the product): 5) a low content of aromatic hydrocarbons in the C5+hydrocarbons not exceeding 5 wt%; 6) high residual content of oxygen-containing compounds in the reaction water to 7 wt.%.

The present invention is to increase the selectivity and productivity of the catalyst in the liquid hydrocarbon.

The problem is solved in that for the catalytic conversion of synthesis gas into hydrocarbonaceous products as catalyst, a mixture of iron catalyst for Fischer-Tropsch synthesis in oxidized or reduced form, promoted by oxides of aluminum, silicon, alkaline or alkaline earth metals, and acid component of the crystalline aluminosilicate ZSM-5,or silicoaluminate type SAPO-5, apply the circulation of the gas stream after reactor volume ratio of the number of circulating gas to the raw synthesis gas, equal 1-1000, and the process is performed at a pressure of 10-100 ATM, a temperature of 220-400oC, space velocity initial synthesis gas 100-5000 h-1, mole inlet to the reactor is from 0.01 to 40%.

Distinctive features of the invention are: (a) for the catalytic conversion of synthesis gas into hydrocarbonaceous products as catalysts is a mixture of iron catalysts for Fischer-Tropsch synthesis in oxidized or reduced form, promoted by oxides of aluminum, silicon, alkaline or alkaline earth metals with acidic components - crystalline aluminosilicates of the ZSM-5,or silicoaluminate type SAPO-5 in weight ratio of iron-containing catalyst/acid component, equal 10-90/90-10; b) the process used circulation of the gas stream after reactor volume ratio of the number of circulating gas to the raw synthesis gas, equal 1-1000; C) process performed at a pressure of 10-100 ATM, a temperature of 220-400oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH original synthesis gas, is equal to 1-3, and volumetric content of CO2in the gas stream at the inlet to the reactor is from 0.01 to 40%;
g) recovering the catalyst for Fischer-Tropsch synthesis is carried out in two variants - or in the composition of the catalytic composition of the synthesis gas at a temperature of 220-400oC, a pressure of 10-100 ATM and about the re at a temperature of 400 to 500oWith the pressure of 50-100 ATM and a flow rate of the circulating hydrogen-containing gas 2000-30000 h-1.

The choice of catalyst for the conversion of synthesis gas to hydrocarbon products based on the fact that all of the catalysts of the Fischer-Tropsch synthesis the most productive in the temperature range 220-400oWith are fused iron catalysts. The combination of fused iron catalysts with acidic components leads to enhanced synthesis of hydrocarbons from H2, Co and CO2due to more rapid reactions of conversion of the intermediate products of the Fischer-Tropsch synthesis (alcohols, olefins) on the acid component in the target hydrocarbon products. Fused iron catalysts (hereafter. as Agrocomplex-1, 2, 3) differ from each other by the method of preparation, quantity and composition of the modifying additives. The acidic components of the catalytic composition differ from each other by the type of crystal structure and acidic characteristics, dependent on the molar relationship SiO2/lO3in the acid component. The ratio between the Agrocomplex and acid component affects the selectivity and performance of the catalytic composition on liquid hydrocarbons.

and CO2due to the following factors. High blood pressure is necessary for deeper conversion of synthesis gas. Lower limit of temperature range (220oC) determined by the minimum activity of the catalyst, the excess of the upper temperature limit (400oC) leads to a rapid superusuario the catalyst surface. The volumetric feed rate of the original synthesis gas is determined by the activity of the used catalyst at a fixed pressure and temperature. The claimed value of the flow rate is optimal for obtaining gasoline and diesel fractions. The ratio between H2and FROM, and between co and CO2is determined by the stoichiometry of chemical reactions synthesis of hydrocarbons. For example, for the formation of the group "CH2" paraffin hydrocarbons on one carbon atom requires two atoms of hydrogen, and the amount of bound "On" in the feedstock determines the consumption of hydrogen in the formation of molecules N2Acting on the Basis of theoretical assumptions, experiments were conducted under conditions sufficiently close to the stoichiometric ratio between "C", "O" and "H". The recovery process of the iron component of the catalyst is required on the via recovery was determined experimentally. Found the conditions of recovery allow to achieve the objectives of the process of synthesis of hydrocarbons below.

An important role in achieving high selectivity and productivity of the catalytic composition according To5+hydrocarbons belongs circulation of the gas stream after separation of the liquid products. First, the continuous removal of water and liquid hydrocarbons from the gas contacting prevents poisoning of the surface of the iron catalyst with water vapor, substantially suppresses the reaction of formation of inactive in the reaction, Fischer-Tropsch, carbon dioxide and decreases the rate of reactions of cracking resulting From the5+hydrocarbons in the acid component. Secondly, when the recycling light olefins and oxygen-containing intermediate products (e.g., dimethyl ether) is repeatedly in contact with the catalyst, into the target products. Thirdly, the high linear velocity of the circulating gas stream in combination with a constant entrainment of excess heat from the area of catalysis positively affect the temperature distribution in the reactor, improve the processes of heat transfer and mass transfer.

Example 1 (the prototype). Fractions processed new synthetic zeolite ZSM-5, mixed in a mass ratio of 56 to 44 and loaded into the flow reactor. The experience carried out at a pressure of 30 ATM, a temperature of 280oC and space velocity of the synthesis gas 2930 h-1. The composition of the original exhaust gases and liquid products of the synthesis were determined chromatographically. Conditions and key indicators of the experience shown in the table.

Industrial applicability of the invention is illustrated by examples 2-16.

Example 2. Charged to the reactor 30 cm3fractions of 0.25-0.5 mm fused iron catalyst Agrocomplex-1 and granulated (30 wt.% Al2About3) zeolite ZSM-5 in a mass ratio of 50/50. The original synthesis gas is fed in the reactor block to mix with the circulating gas block. Reactor unit consists of a reactor with heating, condenser, separator, high and low pressure, intermediate liquid products and an electromagnetic pump for circulating the gas. Before the synthesis of the catalyst is subjected to restore the synthesis gas under the following conditions: a pressure of 10 ATM, the temperature is 350oWith the duration of 24 h; then the rise of pressure up to 30 ATM, and the continuation of the restoration at a temperature of 350oWith the duration of 8 hours After recovery is razran 30 ATM and at a temperature in the catalyst bed 300oC. To prevent accumulation in the reactor block non-condensable products from the block after the high pressure separator continually remove part of the circulating gas. Liquid products (condensed hydrocarbons, water fraction drawn from the reactor building gas and allocated by throttling gaseous hydrocarbons analyzed separately by gas chromatography. Conditions and key indicators of the experience shown in the table.

Example 3. Analogous to example 2. Conditions and key indicators of the experience shown in the table.

Example 4. Analogous to example 2. Characterized in that the catalyst SFT use of fused iron catalyst Agrocomplex-2 and restore spend synthesis gas at a pressure of 30 ATM, a temperature of 350oC for 16 h Conditions and key indicators of the experience shown in the table.

Example 5 Same as example 2. Characterized in that the catalyst SFT use of fused iron catalyst Agrocomplex-3 and restore spend a hydrogen-containing gas in a separate reactor before mixing it with the acid component at a pressure of 100 atmospheres, a temperature of 400 to 500oC and flow rate of the circulating vodorodnij what about 33/67. Conditions and key indicators of the experience shown in the table.

Examples 6-8. Similar to example 5. Conditions and the main results of the experiments are shown in the table.

Example 9. Similar to example 5. Characterized in that the catalytic composition, the mass ratio of Agrocomplex-3/ZSM-5 is 25/75. Conditions and key indicators of the experience shown in the table.

Example 10. Similar to example 5. Characterized in that the catalytic composition, the mass ratio of Agrocomplex-3/ZS-5 is equal to 15/85. Conditions and key indicators of the experience shown in the table.

Examples 11-12. Similar to example 5. Distinguished by the fact that as the acid component used granulated (30 wt.% Al2OC) type zeolite(SiO2/Al2O3=75). and the mass ratio of Agrocomplex-3/equal to 40/60. Conditions and the main results of the experiments are shown in the table.

Example 13. Similar examples 10-11. Characterized in that the catalytic composition, the mass ratio of Agrocomplex-3/equal to 70/30. Conditions and key indicators of the experience shown in the table.

Example 14. Analogous to example 2. The difference is that the catalyst Agrocomplex-1 is subjected to restore the m rise of temperature up to 280oWith and continuation of recovery at this temperature for 4 hours After recovery is the development of a catalyst at a temperature of 300oWith over 20 hours is also Distinguished by the fact that as the acid component used granulated (30 wt.% Al2OC) silicoaluminate type SAPO-5, and the mass ratio of Agrocomplex-3/S-5 is equal to 30/70. Conditions and key indicators of the experience shown in the table.

Examples 15-16. Similar to example 5. Differ that was charged to the reactor 20 cm3fractions of 0.25-0.5 mm fused iron catalyst Agrocomplex-3 and 130 cm3granulated (30 wt.% Al2OC) type zeolite(SiO2/Al2O3=75) in the form of granules of size 34 mm. Differ in catalytic composition mass ratio of Agrocomplex-3/is 45/55. Conditions and the main results of the experiments are shown in the table.

As seen in the results table, the proposed method allows to obtain a liquid (C5+) hydrocarbons and has advantages compared with prototype:
1) the yield of liquid hydrocarbons in the calculation of the original synthesis gas 1.5-2.6 times higher;
2) selectivity coord the catalytic composition on liquid hydrocarbons 1.1 to 2.0 times higher;
5) the productivity per unit volume of iron-containing catalyst (Agrocomplex) is much greater than the values calculated from experimental data of the prototype;
6) in all the examples, the proposed method the degree of beneficial use "carbon" synthesis gas more than 2 times above in the prototype:
7) the content of aromatic hydrocarbons in the C5+the hydrocarbons of the proposed method is significantly higher than in the prototype, which positively affects the octane numbers of the gasoline fractions isolated from liquid hydrocarbons


Claims

1. A method of producing hydrocarbons from carbon oxides and hydrogen, comprising contacting the synthesis gas with a catalytic composition consisting of a mixture of iron catalyst for Fischer-Tropsch synthesis and acid component at elevated pressure and temperature and desired conditions restoration of iron-containing active component of the catalyst composition, characterized in that as the acid component used crystalline aluminosilicate or silicoaluminate use the circulation of the gas stream after the reactor volume is the situation 10-100 ATM, the temperature 220-400oC, space velocity initial synthesis gas 100-5000 h-1, a molar ratio of N2/WITH the source sites gas equal to 1-3, and volumetric content of CO2in the gas stream at the inlet to the reactor is from 0.01 to 40%.

2. A method of producing hydrocarbons under item 1, characterized in that as the iron catalyst for Fischer-Tropsch synthesis are fused iron catalyst in the oxidized or the reduced form, promoted by oxides of aluminum, silicon, magnesium, potassium and calcium.

3. A method of producing hydrocarbons under item 1, characterized in that the acid component of the catalyst used crystalline silicates with the structure of ZSM-5,.

4. A method of producing hydrocarbons under item 1, characterized in that the acid component of the catalyst used crystalline silicoaluminate with the structure of SAPO-5.

5. A method of producing hydrocarbons under item 1, wherein the catalytic composition comprises 10-90 wt. % iron catalyst for Fischer-Tropsch synthesis and 10-90 wt. % of acid component.

6. A method of producing hydrocarbons according to any one of paragraphs. 1-5, characterized in that the no is the temperature 220-400oC, a pressure of 10-100 bar and a space velocity of the synthesis gas 100-5000 h-1.

7. A method of producing hydrocarbons according to any one of paragraphs. 1-5, characterized in that the recovery of the catalyst in the Fischer-Tropsch synthesis is carried out until mixing with the acid component in a separate reactor at a temperature of 400 to 500oWith the pressure of 50-100 ATM and a space velocity of hydrogen containing gas 2000-30000 h-1.

 

Same patents:

The invention relates to a method of manufacturing a synthesis gas, intended for use in the synthesis of gasoline, methanol or dimethyl ether

The invention relates to a Fischer-Tropsch synthesis from carbon monoxide and hydrogen with obtaining alcohols and olefins

The invention relates to a method of preparation of the catalyst and its use in the conversion of synthesis gas in accordance with the Fischer-Tropsch process

The invention relates to a method of manufacturing a synthesis gas used for synthesizing gasoline, kerosene and gas oil by using the reaction system of the Fischer-Tropsch

The invention relates to petrochemistry, in particular to methods for catalytic processing of natural and associated petroleum gas in liquid hydrocarbons

The invention relates to an improved method implementing the reaction of the Fischer-Tropsch process, which consists essentially in carrying out the first stage of the reaction in the reactor gas-liquid-solid fluidized bed and carrying out the second stage of separation, at least partially (inside or outside the unit), suspension of solids in a liquid

The invention relates to organic chemistry, namely to the petrochemical industry, in particular to a method for producing hydrocarbons from a mixture of CO, H2and CO2(hereinafter referred to as synthesis gas)

The invention relates to the production of catalysts for selective reduction of NOx

The invention relates to chemistry
The invention relates to the field of chemistry, and in particular to methods of preparation of catalysts for the conversion of light hydrocarbons to high octane motor fuel components

The invention relates to compositions that can be used for the conversion of hydrocarbons in the C6-C8aromatic hydrocarbon and the olefin, to a method for producing the composition and method of using the composition for the conversion of hydrocarbons in the C6-C8aromatic hydrocarbon and olefin

The invention relates to improved compared with the prior art catalyst to produce liquid hydrocarbons of low molecular weight oxygenated organic compounds comprising crystalline aluminosilicate type pentasil with the value of the molar relationship of silicon oxide to aluminum oxide from 25 to 120, sodium oxide, zinc oxide, oxides of rare earth elements and a binder, where the oxides of rare earth elements it contains the oxides of the following composition, mol.%:

the cerium oxide - 3,0

the oxide of lanthanum - 65,0

the oxide of neodymium - 21,0

the oxide of praseodymium - Rest

moreover, each value of silicon oxide to aluminum oxide in the crystalline aluminosilicate type pentasil corresponds to a certain range of values of the content of sodium oxide, in the following ratio of catalyst components, wt.%:

Crystalline aluminosilicate type pentasil - 63,0-70,0

The sodium oxide - 0,12-0,30

Zinc oxide - 0,5-3,0

The oxide of rare earth elements in the specified composition - 0,1-3,0

Binding - Rest

This catalyst has a higher activity

The invention relates to a method for selective receipt of paraxylene, which includes the interaction of toluene with methanol in the presence of a catalyst containing a porous crystalline aluminosilicate zeolite having a diffusion parameter for 2,2-Dimethylbutane about 0.1-15 sec-1measured at a temperature of 120oC and a pressure of 2.2-Dimethylbutane (8 kPa)

The invention relates to the refining, namely, the processing of the waste refinery gases for obtaining aromatic concentrate to increase the octane characteristics of low-octane straight-run gasoline or gas condensate

The invention relates to a process for production of liquid hydrocarbons enriched ISO - and cycloparaffins, which can be used as an additive in the production of high-octane gasoline with a content of aromatic hydrocarbons of not more than 30 wt.%

The invention relates to catalysts for the conversion of aliphatic hydrocarbons, C2- C6in high-octane gasoline or aromatic hydrocarbons, as well as to methods of transformation of aliphatic hydrocarbon, C2- C6in high-octane gasoline or aromatic hydrocarbons
Up!