A method of converting hydrocarbons and a method of producing catalyst for implementation

 

(57) Abstract:

Scope: the invention relates to the catalytic conversion of hydrocarbons and can be used in chemical, petrochemical and gas industry. The invention: is to carry out the conversion of the hydrocarbon feedstock with an oxidant (steam, carbon dioxide or mixtures thereof) in the presence of a catalyst containing 0.3 to 10.0 wt. % of Nickel oxide supported on a carrier containing oxides of aluminum and/or zirconium containing metal oxides from the group of calcium, barium, strontium when the molar ratio of the oxides of aluminum and/or zirconium and additives is equal to (1-6):1, respectively. The technology of preparation of the catalyst. 2 C. and 8 C.p. f-crystals, 2 tab.

The invention relates to the catalytic conversion of hydrocarbons and can be used in chemical, petrochemical and gas industry.

Two main directions of improving economic efciency of hydrogen production by methane reforming reduction ratio oxidant/carbon and increasing the load. Work on these modes requires the use of catalysts, combining high ACTIA contradict each other.

Known catalyst containing 1-40 wt. Nickel oxide on a carrier, comprising the oxides of magnesium, zirconium and silicon (see USSR author's certificate N 192091, CL 01 J, publ. 1967). As follows from the description, high resistance to superusuario such a catalyst is achieved by using a low content of Nickel oxide, and the high activity of the high content of Nickel oxide. The combination of these two properties is achieved by the combined digester frontal layer, working in conditions of high threat supervivencia loaded catalyst with a low content of Nickel oxide, with the required degree of reforming is achieved by loading a subsequent part of the reactor high activity catalyst with a high content of Nickel oxide. Thus, this catalyst does not solve the problem of combining high resistance to superusuario and activity in the framework of a single catalyst pellet. In addition, the catalyst contains an oxide of silicon, which is unacceptable for a number of modern units steam reforming of methane pressure of 2-4 MPa.

Also known catalyst with a small Nickel content (0.01 to 0.7 wt. ) on a carrier consisting mostly of disposizione it in the modern highly intensive units producing hydrogen, working at space velocities of 2000-3000 h-1. Shown in the patent, the maximum volumetric feed rate convertible mixture is 1000 h-1that is more than 2 times lower than desired. Insufficient activity of the catalysts on the zirconium dioxide is confirmed by the results of later studies (Jens R. Rostrup-Nielsen. "Steam reforming catalysts", Tecknisk Forlag A/S (Danish tecknical press inc. Copenhagen, 1975, p. 125), which was found extremely low specific catalytic activity of Nickel on the carrier zirconium oxide. Obviously, a high resistance to superusuario such a catalyst is also achieved by reducing its activity.

Closest to the invention is a method of converting hydrocarbons, including interaction feedstock with an oxidant in the presence of a Nickel catalyst at elevated temperatures (700-800aboutC). Using the catalyst of the brand GIAP-18 composition, wt. NiO is not less 11,0 Al2O3not less than 70.0 Cao 6-10 (see Catalysts for nitrogen industry, Cherkassy, 1989, S. 6 prototype).

Due to the high content of Nickel oxide catalyst has high activity but low resistance to superusuario (PL. 1). The catalyst Les is receiving catalyst for conversion of hydrocarbons, including the preparation of a carrier by mixing the source of oxides or compounds (Al2O3and Cao), shaping, hydrothermal processing, firing and subsequent impregnation of the support with a solution containing the compound of the Nickel and heat treatment to obtain a catalyst of the above composition (prototype).

The aim of the invention is the creation of a technology process for the catalytic conversion of hydrocarbons, now flowing with a low ratio of oxidant/carbon and obtaining a catalyst having improved resistance to superusuario while maintaining its high activity.

This is solved by a method of converting hydrocarbons, including interaction feedstock with an oxidant in the presence of Nickel-containing catalyst at elevated temperature, in which the interaction is carried out in the presence of a catalyst containing 0.3 to 10.0 wt. of Nickel oxide supported on a carrier containing oxides of aluminum and/or zirconium containing metal oxides from the group of calcium, barium, strontium when the molar ratio of the oxides of aluminum and/or zirconium, and oxides additives equal to (1-6):1 respectively.

The oxidant used and 450 to 950aboutC, a pressure of 0.1-4.0 MPa and a flow rate of hydrocarbons 2000-4000 h-1.

The task is also solved by a method of producing catalyst for conversion of hydrocarbons, including the preparation of a carrier by mixing the source of oxides or compounds of metals, shaping, hydrothermal processing, roasting, subsequent impregnation of the support with a solution containing compounds of Nickel and heat treatment in which the mixture of oxides of aluminum and/or zirconium, or their compounds with additives of oxides from the group of calcium, barium, strontium or mixtures thereof or their compounds is carried out in a molar ratio (1-6): 1, respectively, after which the mixture obtained is formed, calcined at 1350-1500aboutC for 1-8 h, then subjected to hydrothermal treatment and the resulting product is calcined at 120-190aboutWith and impregnating the heated solution containing compounds of Nickel with a concentration of 20-150 g/l in terms of Nickel, followed by heat treatment at 100-550aboutC.

According to the invention, the hydrothermal treatment is carried out simultaneously with the impregnation of the support with an aqueous solution containing compounds of Nickel with a Nickel concentration of 4.0-20.0 wt. in terms of Nickel at 40-100about<-5,0 PM

This hydrothermal treatment is carried out with water or an alkaline or acidic aqueous solution at 40-100aboutC for 1-5 h with stirring, followed by calcining.

The latter is carried out at 200-900aboutC for 0,5-5,0 h

The impregnation or hydrothermal processing media carried out with an aqueous solution containing a compound of Nickel selected from the group: Nickel nitrate, ammonium carbonate or ammonium nitrate complex of Nickel.

In addition, the heat carrier is conducted at 100-550aboutC for 0,5-5,0 h

According to the invention an aqueous solution of compounds of Nickel further comprises a promoter and/or activators.

The advantage of this method is the efficient conversion of hydrocarbons at high catalyst activity and resistance to carburizing.

The essence of the proposed technology consists in the following.

Upon receipt of the catalyst at the stage of hydrothermal treatment is partial hydration of the surface of the medium with formation of a dense ceramic substrate layer hydration products having a very high specific surface. PEFC remove hydrated water. Thus, a dense sintered ceramic substrate layer is formed products with highly developed microporous surface having high wettability. The combination of these factors leads to the fact that in the process of impregnation of the carrier Nickel compound Nickel stabilized on the surface in much dispergirovannom the state, providing high specific catalytic activity of the catalyst. The above properties of the catalyst ensures its high activity at relatively low content of Nickel. The opportunity to reduce the Nickel content in the catalyst allows you to apply the desired amount of Nickel in a single impregnation of the carrier, which greatly simplifies the technology of preparation of the catalyst. The presence of oxides of alkaline earth metals (Ca, Ba, Sr) in the catalyst carrier in the stated quantities leads to the fact that Nickel-containing phase, located on the active surface, is a complex ions of alkaline-earth metals. A characteristic feature of this complex is a high ability to suppress the formation of carbon in the process of conversion of hydrocarbons. The proposed TEI only with high activity, but with high resistance to superusuario, and technology preparation is simple and economical.

Received on the proposed technology is the catalyst in work in process steam, carbon dioxide or paraplegic - pilot conversion of hydrocarbons provides the equilibrium methane concentration in the final gas mixture with a ratio of oxidant/carbon in the reaction mixture at 20-30% below the standard.

The technology is implemented as follows. According to the methods of examples 1-3 is preparing a catalyst for the conversion of hydrocarbons. According to the method of example 4 is the conversion of hydrocarbons with the use of the catalyst.

P R I m e R 1. The mixture to obtain a carrier for the catalyst is prepared by mixing zirconium hydroxide and barium carbonate in a ratio of 1.6:1 by weight. including the Molar ratio of ZrO2:BaO 2:1. Based on the obtained mixture is molded granules media in the presence of a binding 10%-aqueous solution of polyvinyl alcohol. The firing of the pellets produced at 1500aboutC for 4 h Then these granules are subjected to hydrothermal treatment at 100aboutC for 5 h in an aqueous neutral solution with stirring, after which they calcinate is itrate Nickel with a Nickel concentration of 51 g/l upset and heat treated at 550aboutC for 1 h In the result the catalyst with bulk Nickel content of 0.9%

P R I m m e R 2. The mixture to obtain a carrier is prepared by mixing the aluminum oxide and calcium hydroxide in the ratio of 8.3:1 wt.h. parts, respectively. The molar ratio of Al2O3:CaO 6:1. Based on the obtained mixture is molded granules in the presence of a binder. The firing of the pellets is carried out at 1400aboutC for 1 h Annealed pellets are subjected to hydrothermal treatment of an aqueous solution containing Nickel nitrate at a concentration of 12 wt. in terms of Nickel, for 2 h under stirring at 100aboutS, after which the granules prokalyvayutsya 400aboutC for 1 h to obtain a catalyst containing 6.5 wt. Nickel.

P R I m e R 3. The mixture to obtain a carrier is prepared by mixing aluminum oxide, calcium oxide and barium oxide in the ratio of 15:4:1 wt.h. respectively. The molar ratio of aluminum oxide to the oxide of alkaline-earth metals is 1.9: 1. Based on the obtained mixture is molded in the presence of a binder granules media. The firing of the pellets produced at 1450aboutWith over 3 hours of Fired pellets are subjected to hydrothermal treatment of an aqueous solution containing Ego granules prokalyvayutsya at 500aboutC for 1 h and absorb the heated solution containing Nickel nitrate concentrations (Nickel) 20 g/l, with stirring. Then the granules are subjected to heat treatment at 500aboutC for 1 h to obtain a catalyst containing 3.3 wt. Nickel oxide (catalyst 8 table. 1).

Data obtained by the method of example 3, the sample of catalyst are presented in table. 1.

P R I m e R 4. Purified from sulfur natural gas composition, vol. CH498,0; C2H60,4; C3H80,2; CO20,1; inerti of 1.3% with a temperature of 370aboutC, a pressure of 4.0 MPa in the number 38000-43000 nm3/h is mixed with the heated steam with a pressure of 4.1 MPa and a temperature of 380aboutWith the number of 95-115 t/h Molar steam:gas ratio of 3.0:1. The resulting steam-gas mixture is heated to a temperature of 500aboutWith and enters the heated reaction tubes of the tube furnace, filled with a catalyst prepared by the method of example 3. In the tubes at a pressure of 3.0 MPa, space velocity of 2500 h-1(natural gas) and the outlet temperature 770-830aboutWith process steam reforming of hydrocarbons. Dry converted gas after exiting the tube furnace has the following composition, about. CH44-6; the s on the process technology for the conversion of hydrocarbons are presented in table. 2.

The proposed composition and technology of preparation of the catalyst, in comparison with known, provides the following advantages:

to obtain the catalyst, combining high activity, a high resistance to superusuario and stability of physical and mechanical characteristics that determine the effectiveness of its use;

to ensure the above properties of the catalyst, if not more than twofold application of active component in the process of preparation of the catalyst, which greatly improves production efficiency of the catalyst;

to ensure the same high performance characteristics of the catalyst in the range of the content of the active component of 0.3-10.0 wt. which allows to significantly reduce the consumption of Nickel and thereby reduce the production of synthesis gas and to increase economic efficiency and ecological safety of catalysts for the conversion.

1. A method of converting hydrocarbons, including interaction feedstock with an oxidant in the presence of Nickel-containing catalyst at elevated temperature, characterized in that the interaction is carried out in the presence of katalysatoren metal oxides from the group of: calcium, barium, strontium when the molar ratio of the oxides of aluminum and/or zirconium, and oxides additives, is equal to (1 - 6) : 1 respectively.

2. The method according to p. 1, characterized in that as oxalates use water vapor, carbon dioxide, or mixtures thereof.

3. The method according to PP.1 and 2, characterized in that the interaction is carried out at 450 - 950oC, a pressure of 0.1 - 4.0 MPa and a flow rate of hydrocarbons 2000 - 4000 h-1.

4. The method of producing catalyst for conversion of hydrocarbons, including the preparation of a carrier by mixing the source of oxides or compounds of metals, shaping, hydrothermal processing, roasting, subsequent impregnation of the support with a solution containing compounds of Nickel, and heat treatment, characterized in that the mixture of the source of the oxides of aluminum and/or zirconium, or their compounds with additives of oxides from the group of calcium, barium, strontium or mixtures thereof or their compounds is carried out in a molar ratio (1 - 6) : 1, respectively, after which the resulting mixture is molded and fired at 1350 - 1500oC for 1 to 8 h, then subjected to hydrothermal treatment and the resulting product is calcined at 120 - 900oWith and impregnating the heated solution containing the SUP>o
C.

5. The method according to p. 4, wherein the hydrothermal treatment is carried out simultaneously with the impregnation of the support with an aqueous solution containing compounds of Nickel with a Nickel concentration of 4.0 - 20.0 wt.% in terms of Nickel at 40 - 100oC for 0.5 - 5.0 hours under stirring, followed by heat treatment of the product at 100 550oC for 0,5 - 5,0 h

6. The method according to PP.4 and 5, characterized in that the hydrothermal processing him water or alkaline or acid solution at 40 - 100oWith each 1 - 5 h under stirring, followed by calcining.

7. The method according to p. 6, characterized in that the calcination product is carried out at 200 - 900oC for 0,5 - 5,0 h

8. The method according to PP.4 to 7, characterized in that the impregnation or hydrothermal processing media carried out with an aqueous solution containing a compound of Nickel selected from the group: Nickel nitrate, ammonium carbonate or ammonium nitrate complex of Nickel.

9. The method according to PP.4 to 8, characterized in that the heat treatment is conducted at 100 - 550oC for 0,5 - 5,0 h

10. The method according to PP.4 to 9, characterized in that the aqueous solution of compounds of Nickel further comprises a promoter and/or activators.

 

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SUBSTANCE: invention relates to carbon monoxide-water steam conversion to form nitrogen-hydrogen mixture that can be used in ammonia synthesis. Preparation of catalyst comprises precipitation of iron hydroxide from iron nitrate solution with ammonia-containing precipitator, washing of iron hydroxide to remove nitrate ions, mixing with copper compound, granulation, and drying and calcination of granules. Invention is characterized by that iron hydroxide is mixed with copper and calcium oxides at molar ratio Fe2O3/CuO/CaO = 1:(0.03-0.2):(1.0-2.0), after which mechanical activation is performed. Resulting catalyst is 1.8-2.0-fold stronger and by 11.0-15.4% more active than prototype catalyst.

EFFECT: increased strength and catalytic activity.

1 tbl, 3 ex

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SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

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3 cl, 1 tbl, 15 ex

FIELD: industrial inorganic synthesis catalysts.

SUBSTANCE: iron catalyst for ammonia synthesis is reduced via heating of nitrogen/hydrogen mixture to 300-350°C at pressure 0.3-10 MPa, passing it through first activated catalyst bed, which represents 0.2 to 13% of the total volume of catalyst charged into ammonia synthesis column, then through second non-activated iron oxides-based catalyst bed at elevated pressure, whereupon catalyst is aged, temperature and pressure are raised to 425-500°C at pressure 10-20 MPa and catalyst is finally aged to reduce non-activated catalyst bed. Above-mentioned upstream disposed first catalyst bed is low-temperature ammonia synthesis ruthenium catalyst deposited on catalytic carrier.

EFFECT: enhanced process efficiency.

2 cl, 1 tbl, 3 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: passivation of ammonia synthesis catalyst is accomplished via consecutively treating reduced iron catalyst with oxidant at elevated temperatures and process flow rates. Treatment of catalyst with oxidant is commenced with water steam or steam/nitrogen mixture at 150-300°C while further elevating temperature by 50-200°C, after which temperature is lowered to 150-300°C, at which temperature water steam or steam/nitrogen mixture is supplemented by air and treatment of catalyst is continued with resulting mixture while elevating temperature by 50-200°C followed by reduction of catalyst temperature in this mixture to 150-300°C and cooling of catalyst with nitrogen/oxygen mixture at initial ratio not higher than 1:0.1 to temperature 30°C and lower until nitrogen/oxygen mixture gradually achieves pure air composition.

EFFECT: prevented self-inflammation of ammonia synthesis catalyst when being discharged from synthesis towers due to more full oxidation.

6 cl, 1 tbl, 5 ex

FIELD: catalyst preparation methods.

SUBSTANCE: method involves preparing porous carrier and forming catalyst layer by impregnation of carrier with aqueous solution of transition group metal salts followed by drying and calcination. Porous catalyst carrier is a porous substrate of organic polymer material: polyurethane or polypropylene, which is dipped into aqueous suspension of powdered metal selected from metals having magnetic susceptibility χ from 3.6·106 to 150·106 Gs·e/g: iron, cobalt, chromium, nickel, or alloys thereof, or vanadium and polyvinylacetate glue as binder until leaving of air from substrate is completed, after which carrier blank is dried at ambient temperature and then fired at 750°C in vacuum oven and caked at 900-1300°C. Caked blank is molded and then subjected to rolling of outside surface to produce carrier having variable-density structure with density maximum located on emitting area. Formation of catalyst layer is achieved by multiple impregnations of the carrier with aqueous solution of acetates or sulfates of transition group metals: iron, cobalt, chromium, nickel, or alloys thereof in alternative order with dryings at ambient temperature and calcinations to produced catalyst bed 50-80 μm in thickness. In another embodiment of invention, formation of catalyst layer on carrier is accomplished by placing carrier in oven followed by forcing transition group metal carbonate vapors into oven for 60-120 min while gradually raising oven temperature to 850°C until layer of catalyst is grown up to its thickness 50-80 μm.

EFFECT: improved quality of catalyst and reduced its hydrodynamic resistance.

8 cl, 1 tbl, 3 ex

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