Hydrocarbon synthesis catalyst, method for production of c5-c100-hydrocarbons, and a method for preparing catalyst

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 ex

 

The technical field to which the invention relates.

The invention relates to petrochemistry, gas chemistry, coal chemistry and relates to a catalyst for synthesis of hydrocarbons From5-C100from CO and H2, method of producing the specified catalyst and method of producing aliphatic hydrocarbons5-C100using a specified catalyst.

The level of technology

The synthesis of hydrocarbons from CO and H2mainly using cobalt catalysts, because they are selective in respect to the education of linear paraffins. In their presence produces only small amounts of olefins and oxygen-containing compounds. Currently, the attention of researchers is focused on the development of catalysts that are capable of polymerization and a low selectivity for the formation of methane - the main side product of the synthesis.

The ability to polymerization appreciate the value of alpha in equation Schulz-Flory, describing the molecular weight distribution of the resulting hydrocarbons:

Wn=(1-α)2·n·αn-1,

where Wn- mass fraction of BC paraffin with the number of carbon atoms n, n is the number of carbon atoms, α - constant characterizing the probability of growth of hydrocarbon chains. Than Bo is the more α the more selective is the catalyst in relation to the formation of heavy products. For example, if α=0,9 fraction of solid paraffins (C19+in the products of synthesis is 40%.

Known catalysts for carrying out the synthesis of high molecular weight hydrocarbons from CO and H2containing as an active ingredient cobalt and γ-alumina as a carrier (U.S. patent No. 4801573, 5028634, 6271432, European patent application EP 0313375). However, in the presence of these catalysts synthesis takes place with not enough low selectivity for the formation of methane, which reaches 14%.

In most cases, the starting material for the production of γ-aluminum oxide (Al2O3is the boehmite AlO(OH). γ-alumina finds greatest application in catalysis and, in particular, in the synthesis of hydrocarbons from CO and H2. Typically, the catalysts based on γ-Al2About3prepare drawing of metals (in particular cobalt on alumina by impregnation in several stages with solutions of metal salts followed by calcination after each stage, to consolidate the active metal on the carrier.

Catalysts With/γ-Al2About3used for the synthesis of hydrocarbons from CO and H2, characterized by high sensitivity to temperature changes that is due to the specific structure of the media. It is known that γ-Al2About3has a spinel structure, in which aluminum atoms are located partially in the tetrahedra, and partly in the octahedra. When the interaction of cobalt with aluminum oxide, the cobalt atoms can replace the aluminum atoms in the two positions (Journal of Catalysis, 1985, v.93, p.38). Heat treatment of such a catalyst (annealing, recovery, hydrothermal processing) leads to increased interaction of cobalt with aluminum oxide with primary education trudnovosplamenjaemy spinel CoAl2O4.

For example, the famous Co-catalysts based on alumina containing spinel (patent EP 1239019, claim US 2004/0204506). They are distinguished by a lack of activity, since the formation of spinel and spieleubersicht structures leads to a decline in the rate of recovery of cobalt and, as a consequence, to reduce the active surface of the catalyst.

Closest to the proposed invention the catalyst is a catalyst for synthesis of hydrocarbons From5-C100from CO and H2cobalt-based, developed by ConocoPhillips (US2004/0132833 A1), which contains as a carrier stable under hydrothermal conditions γ-alumina. The method thereof includes thermal treatment of boehmite with obtaining γ-aluminium oxide, which is impregnated in several stages causing the nitrate of cobalt. In addition to cobalt and γ-Al2About3known catalyst contains a noble metal of group VIII (Pt or Ru), contributing to the recovery of cobalt from mixed oxides of cobalt and aluminum, and/or some other promoters, which are also introduced into the catalyst by impregnation. However, the proposed catalytic system is not sufficiently low selectivity for the formation of methane, which is 8-10%, and in some cases reaches 15-20%.

Disclosure of inventions

The proposed invention aims at creating a catalyst for synthesis of hydrocarbons From5-C100having high activity and selectivity for the formation of hydrocarbon products with high molekulyarnym weight, as well as increased resistance to changes in temperature, and method of producing such a catalyst, providing a slight interaction of cobalt with the media.

In accordance with this object of the proposed invention is a catalyst for synthesis of hydrocarbons From5-C100containing carrier based on alumina obtained from aluminum hydroxide with the structure of gibbsite, and cobalt, the content of which is 15-50 wt.%.

In the particular case of the invention, the catalyst further comprises a metal VI-VIII groups of the Periodic table DI Mendeleev.

Another object of the invention is a method of producing hydrocarbons From5-C100by conversion of CO and H2in the presence of the aforementioned catalyst having high activity and selectivity for the formation of hydrocarbon products with high molecular weight and low selectivity for the formation of by-product methane. The probability of chain growth generated hydrocarbons With5-C100calculated by the equation Schulz-Flory, is 0.9 to 0.97.

Another object of the proposed invention is a method of producing catalyst for synthesis of hydrocarbons From5-C100that includes the preparation of a carrier by mixing compounds of cobalt with aluminum hydroxide calcination, impregnation in two or more stages of the media on the basis of aluminum oxide in an aqueous solution of cobalt salts and heat treatment, while the use of aluminum hydroxide with the structure of gibbsite, and compounds of cobalt and aluminum hydroxide are mixed in a dry form, with the molar ratio of cobalt and aluminum is from 1:1 to 1:30.

Heat treatment can be carried out by drying and/or calcination.

In a particular embodiment of the invention impose additional promoters by impregnation of the support with solutions of their sole is. The promoters used metals VII-VIII groups of the Periodic table DI Mendeleev.

The implementation of the invention

The method of obtaining cobalt-aluminum catalyst proposed in the present invention is a mechanical mixture of parts of cobalt in the form of its salts and aluminum hydroxide with the structure of gibbsite with subsequent annealing for the formation of a layer that prevents the formation of trudnovosplamenjaemy spinel CoAl2O4, followed by a subsequent (second, third, etc.) stage impregnation with a solution of cobalt salts to make the remaining cobalt content of 15-50 wt.%, preferably 20-40 wt.%, with intermediate stages of drying and calcination.

It is established that the use of catalyst, corresponding to the invention, in the synthesis of hydrocarbons from CO and H2leads to high selectivity to hydrocarbons5+(about 90%) and low selectivity to methane (less than 5%). It should be noted that produce mainly contains normal paraffins (about 80%). The catalyst has a high polimerizuet ability: value αcalculated by the equation Schulz-Flory, 0.9 to 0.97, while the share of hydrocarbons11+the products of synthesis is 80-85%.

At the first stage of preparation of the catalyst as a compound of cobalt IP is allsouth oxide, nitrate, formate, carbonate, basic carbonate, acetate, acetylacetonate, etc. Connection cobalt containing 5-20 wt.% metal (preferably 10-15 wt.%). mechanically (manually or using mechanical sieving machine) is mixed with aluminum hydroxide and calcined within 1-24 hours (preferably 5-15 h) at a temperature of 350-1000°With (preferably 500-1000°). The remaining part of the active component (cobalt) is applied by impregnation in several stages from a solution of salts of cobalt nitrate, acetate, formate, acetylacetonate, etc.). At each stage, the sample is dried on a water bath and the resulting catalyst precursor is dried and/or calcined in a stream of air at a temperature of from 100 to 1000°With (preferably 300-500° (C) for 0.5-10 hours, preferably 1-5 hours).

Before synthesis, the sample of catalyst activated by recovering in a stream of hydrogen at a temperature of 300-600°With (preferably 350-500° (C) for 0.5 to 5 hours (preferably 0.5 to 2.5 hours).

The synthesis of hydrocarbons from CO:H2carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 1-50 atmospheres (preferably 10-30 ATM) and a temperature of 150-300°With (preferably 180-230°). The molar ratio of CO:H2in the synthesis gas is 1:1-3 (preferably 1:2).

Example 1.

Sample catalyst composition 32% Co/Al2the 3prepared in three stages as follows.

1 stage. Carbonate cobalt mechanically mixed with aluminum hydroxide with the structure of gibbsite from the calculation of Al/Co=6 (mol.). Then calcined in a muffle at T=600°C for 10 hours by means of XRD (x-ray phase analysis at this stage is not fixed to the formation of spinel CoAl2O4.

stage 2. of 18.5 g of cobalt nitrate dissolved in distilled water and added to 30 g of the material obtained in stage 1. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined at a temperature of 400°C for 1 h

3 stage. of 18.5 g of cobalt nitrate dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Before synthesis, the sample of catalyst was activated in a stream of hydrogen at a temperature of 350-600°With (preferably 400-450°C) for 1 h Synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at atmospheric pressure in the temperature range 150-220°using synthesis gas composition WITH/N2=1/2(mol.).

Examples 2, 3 and 4.

The method of preparation of the catalyst carried out according to Example 1 except that the first stage contribute cobalt ratio of Al/Co equal to 12, 9 and 3 mol.), respectively. In this case, the total content of cobalt in the catalyst is 27, 29 and 38%, respectively.

Example 5.

The method of preparation of the catalyst carried out according to Example 1 except that for the preparation of media used digidrirovanny aluminum hydroxide with the structure of boehmite. The xfa stage 1 preparation of the catalyst registered education spieleubersicht structures.

Example 6.

The method of preparation of the catalyst carried out according to Example 1 except that at the first stage of preparation of the catalyst used nitrate of cobalt, as well as in the second stage.

Example 7.

Sample catalyst composition 32%to 0.5%Re/Al2O3prepared in four stages as follows.

1 stage. Carbonate cobalt mechanically mixed with aluminum hydroxide with the structure of gibbsite from the calculation of Al/Co=6 (mol.). Then calcined in a muffle at T=600°C for 10 hours by the Method of x-ray fluorescence analysis at this stage is not fixed to the formation of spinel CoAl2O4.

stage 2. of 18.5 g of cobalt nitrate dissolved in distilled water and added to 30 g of the material obtained in stage 1. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined at a temperature of 400°C for 1 h

3 stage. 0.21 g of perrhenate ammonium dissolved in di is fillerbunny water and add to the material, obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined at a temperature of 450°C for 1 h

stage 4. of 18.5 g of cobalt nitrate dissolved in distilled water and added to the material obtained in stage 3. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Before synthesis, the sample activated in a stream of hydrogen at 450°C for 1 h Recovery and testing of a sample of the catalyst is carried out in accordance with the procedure outlined in Example 1.

Example 8.

Using the catalyst obtained and activated in the manner described in Example 6.

The synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 20 atmospheres in the temperature range 150-250°using synthesis gas composition WITH/N2=1/2(mol.).

Example 9.

Using the composition and method of preparation of the catalyst described in Example 7, except that instead of Re apply Pd. Activation and conditions of the synthesis is carried out in accordance with the procedure outlined in Example 1.

Example 10.

Using the composition and method of preparation of the catalyst described in Example 7, except that instead of Re apply EN. Activation and conditions of the synthesis is carried out in accordance with the procedure outlined in Example 1.

The results of the s test samples of catalysts, obtained and tested in accordance with Examples 1-10, shown in the Table below.

Table

Indicators for the synthesis of hydrocarbons from CO and H2conducted using samples of the catalysts corresponding to the invention
ExampleThe CO conversion,%Selectivity for CH4,%The selectivity for C5+,%[C11+], wt.%α
158393860,92
266489810,91
358492830,91
467687840,91
5362940840,93
664584840,94
790488760,88
866493830,91
9 60781710,87
1081879610,83

The table below shows results show that the proposed method of preparation of the cobalt catalyst results in catalytic systems, characterized by high selectivity for the target product (about 90%) and allowing to obtain hydrocarbons with high molecular weight (α>0,9) low selectivity of the formation of by-product methane (generally less than 5%).

1. Catalyst for synthesis of hydrocarbons From5-C100containing carrier based on alumina obtained from aluminum hydroxide with the structure of gibbsite, and cobalt, the content of which is 15-50 wt.%.

2. The catalyst according to claim 1, characterized in that it further contains metals VII-VIII groups of the Periodic table of Mendeleev.

3. A method of producing hydrocarbons From5-C100by catalytic conversion of CO and H2, characterized in that the catalyst used, the catalyst according to claim 1 or 2.

4. The method of producing catalyst for synthesis of hydrocarbons From5-C100that includes the preparation of a carrier by mixing compounds of cobalt with aluminum hydroxide and calcination, p is Opieki in two or more stages of the media on the basis of aluminum oxide in an aqueous solution of cobalt salts and heat treatment, characterized in that the use of aluminum hydroxide with the structure of gibbsite, and compounds of cobalt and aluminum hydroxide are mixed in a dry form, with the molar ratio of cobalt and aluminum is from 1:1 to 1:30.

5. The method according to claim 5, characterized in that the heat treatment is carried out wyszukiwanie and/or roasting.

6. The method according to claim 5, characterized in that impose additional promoters by impregnation of the support with a solution of their salts.

7. The method according to claim 6, characterized in that as promoters use metals VII-VIII groups of the Periodic table of Mendeleev.



 

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1 tbl, 12 ex

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5 cl, 2 tbl, 6 ex

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3 tbl

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

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3 cl, 1 tbl, 13 ex

FIELD: petrochemical process catalysts.

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EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

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