Method of preparing fischer-tropsch catalyst for synthesis gas conversion process

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

 

The present invention relates to the field of synthesis of hydrocarbons from CO and H2in particular to catalysts and methods for their preparation, for the synthesis of hydrocarbons From5and above by the reaction of the Fischer-Tropsch and can be used in the petrochemical industry.

The invention solves the problem of developing a method of making an effective catalyst for the conversion of synthesis gas into hydrocarbons.

It was made many attempts to create effective catalysts for the selective conversion of synthesis gas into hydrocarbons.

A known method of producing catalyst for synthesis of hydrocarbons, C1-C11/Patent RF №2100332, 07 C 1/04, 1997/, in which the fraction With5+enriched with ISO, mainly isopentane and isohexane. Catalyst for synthesis of hydrocarbons obtained by mixing the calcined zeolite with zinc-chromium component in a mass ratio of 1:5-1:1 and pelletizing the mixture with the addition of 2-3 mol.% graphite. Then the catalyst is slowly heated in a reducing environment (a mixture of methanol, hydrogen or synthesis gas with an inert diluent) to a temperature of 380-400°With the purpose of forming an active chromite zinc.

A known method of producing a catalyst for the conversion of synthesis gas to Fischer-Tropsch containing a mixture of two transition elements, such as Cu, Zn and/or Cr, and the crystal is ical aluminosilicate type zeolite of the mordenite /U.S. Patent No. 4500646, B 01 J 029/18, B 01 J 029/24, 1989/, including mechanical mixing of two transition metals in oxidized form, selected from the group consisting of copper, zinc and chromium with the mordenite in hydrogen form, the impregnated mordenite nitrate zinc, and use the mordenite obtained by the sequential processing dealumination in an acidic environment.

The disadvantages of this method of cooking is its technological complexity, namely, that for the preparation of the catalyst, of active and selective in obtaining hydrocarbon composition With5the mordenite previously subject to an additional stage of dealumination - chemical and hydrothermal.

A known method of producing a catalyst for a process of the Fischer-Tropsch synthesis containing zeolite (ZSM-5 or ZSM-11 or ZSM-12 or ZSM-35 or ZSM-38) and the active component - With - /U.S. patent No. 5104902, 01 1/04, 1992/, which is obtained by impregnation of the zeolite component with an aqueous solution of cobalt nitrate in a ratio of 100 parts by weight of cobalt per 1000 parts by weight of the catalyst, followed by stirring under vacuum, drying, using microwave radiation, roasting and pressing with obtaining fractions 1-2 mm.

The disadvantages of this method of preparation of the catalyst is large, the time spent is passed in its preparation, technological complexity associated with the application of vacuum and microwave radiation, due to the strict limitation of the size of the zeolite crystals is not more than 5 microns and the introduction of additional promoter - thorium, to obtain the necessary activity and selectivity in the conversion of synthesis gas.

The closest in technical essence and the achieved effect is the catalyst for the conversion of synthesis gas and the method of its preparation /U.S. Patent No. 5126377, C 07 C 1/04, 1992/. Get the hydrogen form of ZSM-5 double processing 1 M solution of ammonium nitrate or twice the processing of 1 M HCl solution followed by calcining at 550°C. Then dictionarie zeolites impregnated with the necessary quantities of solutions of cobalt nitrate, thorium nitrate and chromium nitrate. The impregnated zeolite is stirred under vacuum for 30 min, dried using microwave radiation, and then calcined at 500°C for 4 hours. The catalyst is pressed and select the fraction 1-2 mm for catalytic tests.

The disadvantages of this method of preparation of the catalyst are also a large amount of time spent on its preparation, which is associated with the application and the active component, and a promoter (thorium or chromium), and technological complexity.

The task of the invention is the creation of the of procedure, reduce the time of cooking by reducing the stages of preparation of the catalyst while maintaining the high level of conversion of synthesis gas, increasing the yield of hydrocarbons with small allocation of CO2and methane.

This object is achieved in that in the known method of preparation of the catalyst for the conversion of synthesis gas to Fischer-Tropsch, including the decationization of the zeolite, the application of active component and modifier, drying and calcination of the obtained catalyst, the decationization is subjected to ' green ' the ZSM-12 in tetraethylammonium form (TEA, Na) at pH 5-9, then dictionary zeolite (30-70 wt.%) mixed with a binder, aluminum oxide with simultaneous introduction at the stage of mixing the active ingredient With - 7.5 to 11.5 wt.% and modifier, which is used as the boron oxide In2About3- 3-5 wt.%

The proposed method for the preparation of the catalyst the conversion of synthesis gas to Fischer-Tropsch is as follows.

Zeolite ZSM-12 in Thea form decationized in 0.5 M ammonium nitrate solution at a temperature of 80°C for 2 hours while the pH of the solution equal to 5-9. The ratio of the volume of the zeolite: solution = 1:4. Dictionary zeolite is separated from the solution by decantation, washed with distilled water. The desired residual content of sodium in the zeolite - IU is its 0.1% is achieved after two treatments with ammonium nitrate solution. As in the process of conversion of synthesis gas to Fischer-Tropsch produce large amounts of water, for increasing the durability of the catalyst in the catalyst composition is injected boron oxide in the amount of 3-5%. We found that changes in the content of boron oxide in the specified interval does not affect the activity and selectivity of the catalyst. In the kneading machine download the necessary amount of aluminum hydroxide (pellet boehmite, humidity 80%), with constant stirring, add the calculated amount of boric acid (when the calcining is decomposed into boron oxide In2About3), zeolite ZSM-12, the resulting double decationization, and cobalt nitrate Co(NO3)2·6N2O. are Stirring 30 minutes, then with continuous stirring of the obtained catalyst mass peptizer solution of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules provalivajut on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour.

Catalytic testing of the samples is of utilizatorul was performed in a flow reactor with a fixed catalyst bed at a pressure P 2 MPa, space velocity of the synthesis gas Vo=1000 h-1(the molar ratio of N2/CO=2), temperature 240°C. the efficiency of the catalyst was evaluated by the CO conversion and selectivity of the formation of CO2CH4, hydrocarbons With2-C5and hydrocarbon composition above >5.

The invention is illustrated by the following examples.

Examples 1-5. Zeolite ZSM-5 calcined in a stream of air to remove the organic component at 500°With, then spend twice decationization or 1 M solution of ammonium nitrate, or a 1 M solution of hydrochloric acid. After decationization zeolite calcined at 550°4 hours. The obtained zeolite impregnated with aqueous solutions of the respective salts nitrates of cobalt, thorium and/or chromium. The catalyst is stirred under vacuum for 30 minutes, dried in a microwave oven and calcined in air flow at 500°4 hours, after which the catalyst was pressed and selected for catalytic tests the size of the granules of catalyst equal to 1-2 mm. Catalytic tests carried out in the microreactor. The catalyst pre-restore in a stream of hydrogen at atmospheric pressure at a temperature of 350°16 hours. The catalysts were tested in the conversion of synthesis gas with a molar ratio of N2/CO=2, temperature 240°C, a pressure of 2 MPa, Vo=1000 h-1. The obtained data are presented in table 1.

Example 6. 30 g of zeolite ZSM-12 (silicate module SiO2/Al2O3=100) NH4-, TEA-form mixed with the pellet of aluminum hydroxide (humidity 80%), which contains 59.5 g of dry alumina add with constant stirring 5.6 g of boric acid (in terms of B2O3=3 g) and 35.3 g of salt of cobalt nitrate Co(NO3)2·6N2O (in terms of Co - 7.5 g) With(NO3)2·6H2O. are Stirring 30 minutes, then with continuous stirring of the obtained catalyst mass peptizer 5-7 ml of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules provalivajut on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour. The composition of the finished catalyst and the results of the catalytic tests are presented in table 1.

Example 7. 50 g of ZSM-12 (silicate module SiO2/Al2O3=120) NH4-, Thea-form mixed with the pellet of aluminum hydroxide (humidity 80%), which contains 37.5 is dry aluminum oxide, add with constant stirring 9.3 g of boric acid (in terms of In2O3=5 g) and 35.3 g of salt of cobalt nitrate Co(NO3)2·6N2About (in terms of Co - 7.5 g). Mixing lead 30 minutes, then with continuous stirring of the obtained catalyst mass peptizer 5-7 ml of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules provalivajut on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour. The composition of the finished catalyst and the results of the catalytic tests are presented in table 1.

Example 8. 30 g of zeolite ZSM-12 (silicate module SiO2/Al2O3=100) NH4-, Thea-form mixed with the pellet of aluminum hydroxide (humidity 80%)containing 55.5 g of dry alumina add with constant stirring 5.6 g of boric acid (in terms of In2O3=3 g) and 54.1 g of salt of cobalt nitrate Co(NO3)2·6N2About (in terms of Co - 11.5 g). Mixing lead 30 minutes, after which a continuous peremeci the years of the obtained catalyst mass peptizer 5-7 ml of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules provalivajut on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour. The composition of the finished catalyst and the results of the catalytic tests are presented in table 1.

Example 9. 50 g of ZSM-12 (silicate module SiO2/Al2O3=100) NH4-, TEA-form mixed with the pellet of aluminum hydroxide (humidity 80%)containing 34.5 g of dry alumina add with constant stirring 7.4 g of boric acid (in terms of B2O3=4 g) and 54.1 g of salt of cobalt nitrate Co(NO3)2·6N2O (in terms of Co - 11.5 g). Mixing lead 30 minutes, then with continuous stirring of the obtained catalyst mass peptizer 5-7 ml of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules PR is valueout on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour. The composition of the finished catalyst and the results of the catalytic tests are presented in table 1.

Example 10. 70 g of zeolite ZSM-12 (silicate module SiO2/Al2O3in NH4-, Thea-form mixed with the pellet of aluminum hydroxide (humidity 80%), which contains 13.5 g of dry alumina add with constant stirring 9.3 g of boric acid (in terms of In2O3=5 g) and 54.1 g of salt of cobalt nitrate Co(NO3)2·6N2O (in terms of Co - 11.5 g). Mixing lead 30 minutes, then with continuous stirring of the obtained catalyst mass peptizer 5-7 ml of 60%nitric acid. Mixing the obtained catalyst mass are within 0.5-1.0 hours, after which excess water is evaporated in a kneading machine, stopping stirring, and then molded by extrusion in the form of cylindrical pellets with a diameter of 1-2 mm, the Obtained granules provalivajut on the air for 10-12 hours at room temperature and calcined in a stream of air for 4-6 hours, slowly raising the temperature of calcination ˜100 deg/hour. The composition of the finished catalyst and the results of the catalytic tests are presented in table 1.

As can be seen from the table, the catalysts based on zeolite ZSM-12 is more selective in the mod is the reattaching the hydrocarbon composition of C5 and above.

The proposed method for the preparation of the catalyst for Fischer-Tropsch synthesis can significantly reduce the time of preparation of the catalyst, bringing together in one stage of the cooking medium, the application of active component and modifier, while maintaining the necessary catalytic characteristics. In addition, the proposed method is an environmentally safe method of preparation of the catalyst, as in this case there are no waste water, which are always present when applying the active component by impregnation, coprecipitation and ion exchange.

Table 1
Conversion of synthesis gas into hydrocarbons N2/CO=2 (molar); Vo=1000 h-1P=2 MPa, T=240°
# exampleThe catalyst composition, wt.%Toco, %Selectivity, %
ZeoliteCoIn2About3ThCrAl2About3CO2CH4(C2-C5)>With5
1ZSM-5 (92.5)7.5-- --451222056
2ZSM-5 (92)7.5--0.5-561161766
3ZSM-5 (92)7.5-0.5--512211859
4ZSM-5 (91.5)7.5-0.50.5-722181564
5ZSM-5 (0)7.5---100465181860
6ZSM-12 (30)83--59.5481.815.21568
7ZSM-12 (50)85--37.5521.315.01568.7
8ZSM-12 (30)12 3--55.5791.514.51569
9ZSM-12 (50)124--34.5811.314.01668.7
10ZSM-12 (70)125--13.3721.014.21767.8

The preparation method of catalyst for the conversion of synthesis gas to Fischer-Tropsch, including the decationization of the zeolite, the application of active component is cobalt and modifier, drying and calcination of the obtained catalyst, characterized in that the decationization is subjected to ' green ' the ZSM-12 in tetraethylammonium form (TEA, Na) at pH 5-9, then dictionary zeolite (30-70 wt.%) mixed with a binder, aluminum oxide with simultaneous introduction at the stage of mixing the active ingredient With - 7.5 to 11.5 wt.% and modifier, which is used as the boron oxide In2About3- 3-5 wt.%.



 

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6 ex, 1 tbl, 1 dwg

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method for preparing double metal cyanide catalysts effective to catalyze synthesis of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms. Method is characterized by that aqueous solutions of metal salt and metal cyanide salt are first brought to react in presence of organic complex ligands and, if necessary, one or several other complexing components to form dispersion of double metal cyanide catalyst, which is filtered to give filtration precipitates. The latter are washed with one or several aqueous or nonaqueous solution of organic complex ligands in flowing washing mode and, if necessary, one or several other complexing components, after which washed filtration precipitates are dried after optional squeezing and mechanical removal of moisture. Washing and drying stages are performed on the same filter.

EFFECT: significantly simplified process due to avoided repetitive redispersing of catalyst followed by transferring filtration precipitate to another equipment.

9 cl, 13 ex

FIELD: various-destination catalysts.

SUBSTANCE: invention relates to production of copper-zinc-aluminum catalysts appropriate for low-temperature steam conversion of carbon monoxide, low-temperature methanol synthesis, and hydrogenation-dehydrogenation of various organic compounds. Catalyst preparation process comprises preparing ammonia-carbonate solutions of copper and zinc, treating aluminum-containing raw material with ammonia-carbonate solution of zinc, mixing thus treated or its mixture with untreated aluminum-containing raw material with copper and zinc compounds, holding resulting suspension in reactor at elevated temperature and stirring, separating formed catalyst mass from solution, drying, calcination, and granulation. Specifically, treatment of aluminum-containing raw material with ammonia-carbonate solution of zinc is carried out at 75-90°C and is followed by ageing at stirring until ammonia-carbonate solution of zinc is decomposed and mixing of copper, zinc, and aluminum-containing raw material is conducted in dosed manner while maintaining reactor temperature 75-90°C and specified copper-to-zinc ratio in liquid phase of suspension. Moreover, zinc compounds are introduced into reactor in the form of ammonia-carbonate solution or oxide, or basic carbonate and copper compound in the form of ammonia-carbonate solution so that copper-to-zinc atomic ratio in finished catalyst is (0.55-2.2):1 and atomic content of aluminum ranges from 2.6 to 10.6.

EFFECT: simplified catalyst preparation technology, avoided noxious effluents and gas emissions, and assured preparation of high-activity, stable, and strong catalysts.

3 cl, 1 tbl, 16 ex

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

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