Catalyst and method of obtaining synthetic gas from carbon dioxide conversion of methane

FIELD: chemistry.

SUBSTANCE: present invention pertains to chemical industry, particularly to catalysts used for converting natural gas, and can be used in petrochemical and oil-refining industry for making catalysts and in gas synthesis process. Description is given of a catalyst, containing a nickel aluminide matrix, inside of which nickel and molybdenum are dispersed, with the following ratio of components, in wt %: Ni3Al - 80-90, Ni - 5-10, Mo -2-10. The catalyst is obtained through self-propagating high-temperature synthesis and is used in the process of carbon dioxide conversion of methane.

EFFECT: high catalytic activity and stability of the catalyst.

2 cl, 4 tbl, 3 ex

 

The invention relates to the chemical industry, in particular to catalysts used for the conversion of natural gas, namely catalysts for reactions involving C-H communication hydrocarbons and help break these ties with the formation of compounds containing multiple bonds (CO) and hydrogen, a mixture called synthesis gas, and the ways carbon dioxide conversion, and can be used in petrochemical, oil refining and other industries for the production of catalysts and process for production of synthesis gas. In the future, the resulting synthesis gas can be widely used in large-scale chemical processes, such as synthesis of dimethyl ether (DME), methyl methacrylate, alcohols, aldehydes, and other Derived dimethyl ether can be used as an environmentally friendly fuel for diesel engines without significant changes in their designs.

Traditionally, the synthesis gas is produced by the methods of steam, propakistani, steam-air or steam-oxygen conversion of hydrocarbons. The composition of the produced synthesis gas depends on temperature, pressure holding process, the used catalyst, the ratio of pairs of initial components, flow rate, composition of the original mixture components. Typically, the source of hydrocarbon raw materials (p is irony gas) purified from sulfur compounds.

The disadvantages of conventional methods for the production of synthesis gas by catalytic conversion of hydrocarbons, are the use of insufficiently active and stable catalyst having relatively large dimensions, large aerodynamic resistance of the granular layer, limitations on the supply of heat in the reaction zone, the need to use oxygen in the mine reactors, restrictions on the possibility of production of small capacity.

The authors M.C.J. Bradford and M.A. Vannice offer for the process of carbon dioxide conversion to use as catalysts, for example, Nickel catalysts using a variety of media on a ceramic base, but often they are exposed to significant superusuario (M.C.J. Bradford and M.A. Vannice. CO2reforming of methane. Catal. Rev. - Sci. Eng., 1999, v.41, p.1-42).

In the works (J.B. Claridge, A.P.E. York, Brungs A.J. e.a. Journal of catalysis, 1998, v.180, No. 1, p.85-100; WO 02076885, J. Sehested, C.J.H. Jacobsen, S. Rokni, and J.R. Rostrup-Nielsen. Activity and Stability of Molybdenum Carbide as a catalyst for CO2Reforming, Journal of Catalysis, 2001, v.201, p.206-212) is shown the possibility of using carbides of Mo and W as catalysts ACM. However, despite the high activity in all three reactions the conversion of methane, a significant drawback is the implementation of the process only at high pressures - at ordinary pressures carbides is ezantivirus due to oxidation of the oxides MO 2.

It is known that catalysts for carbon dioxide reforming of methane can be oxides (RF patent 96100764, 1998; Krylov, O.V., Mamedov AH Heterogeneous catalytic reactions of carbon dioxide. Uspekhi khimii, 1995, v.64, No. 9, s-959). Known and such, which consist of oxide media (Al2About3, SiO2, ZrO2, BaO, CaO and others) and coating of metals (Pt, Pd, Ru, Rh, Ni and others) even Though they have sufficient activity, they are being subjected to coking. Over time, this leads to deactivation of the catalysts that require regeneration and increases production costs. A disadvantage of the known catalysts and carriers is that at high temperatures under conditions of redox environment they are oxidized, which significantly reduces the strength of the contact between particles.

Currently, one of the main directions in solving search catalysts UKM is the development of improved Nickel systems, which would contribute to the kinetic inhibition of formation of carbon on their surface under conditions that thermodynamically favorable for pleodorina. In combination with suitable carriers, such as La2O3, MgO, TiO2and CEO2; using effective promoters, including La2O3, LiO2and even oxide W is found as well as new methods of cooking, such as a method of crystallization in the solid phase, Sol-gel method, citrate method (Krylov, O.V. Heterogeneous catalysis. M: academkniga, 2004, 679 S.; Y.H. Hu, E. Ruckenstein Catalytic Conversion of Methane to Synthesis Gas by Partial Oxidation and CO2Reforming. Adv. Catal., 2004, v. 48, p.297-345; Tomishige K. Syngas production from methane reforming with CO2/H2O over NiO-MgO solid solution catalyst in fluidized bed reactors. Catal. Today., 2004, v. 89, p.405-418; Hao Z., Zhu H.Y., Lu G.Q. Zr-Laponit pillared clay-based nickel catalysts for methane reforming with carbon dioxide. Appl. Catal., 2003, v.242, p.275-286).

At the present time there is no industrial technology for production of synthesis gas by carbon dioxide methane conversion. Existing development is often based on Nickel catalysts used in the process of steam reforming, they do not have sufficient selectivity and quickly deactivated due to the formation of carbon, which covers the active metal centers during catalysis, and accumulate in the pores of the catalyst, causing destructive changes and ultimately decontamination.

The process of carbon dioxide conversion of methane is carried out at high temperatures so the surface area of the catalysts will inevitably decrease. One of the most important requirements of such catalysts is resistant to temperature extremes, thermal shock. It is desirable that they had raised the th thermal conductivity to reduce the possibility of local overheating. These properties are some of the intermetallic compounds of transition metals, for example Nickel, which are widely used to obtain the skeleton of Raney Nickel.

In the literature, there are practically no data on the use of the catalysts of intermetallic compounds for the process of carbon dioxide conversion of methane.

The closest to the achieved result and the technical nature of a catalyst obtained samariterstrasse high-temperature synthesis (SHS) and consisting of intermetallic matrix Ni3Al, in which the dispersed Nickel free (Laurita, Tshernova, Lavalina and other carbon dioxide conversion of methane on Nickel aluminides. The journal of physical chemistry a, 2006, t, No. 8, s-1406). Among the investigated intermetallic systems Ni-Al the highest catalytic activity comparable with commercial steam reforming catalyst, showed this composition Ni3Al, which is provided at a temperature of 1223 To the conversion of CO282.2%, and CH479.6%. The yield of synthesis gas was CO - 43.1 mol.%, H2- 37.8%. Known catalyst obtained high-performance and economical method SVS from compacted mixture of powders of Nickel and aluminum in the form of rods, which are then crushed and sieved to obtain a desired fraction.

However, after catalytic research is known as the catalyst is observed pleodorina, followed by the formation of a carbide of Nickel and graphite-like carbon, which leads to the fact that the catalyst activity is reduced (the catalyst is deactivated).

The present invention is the development of an effective catalyst, resistant to temperature extremes and thermal shock, has a high thermal conductivity to reduce the possibility of local overheating, excluding pleodorina in the process carbon dioxide methane conversion and productivity-enhancing process.

The problem is solved by using as catalyst for carbon dioxide methane conversion material obtained samariterstrasse high-temperature synthesis and containing matrix aluminide Nickel, in which the dispersed Nickel and molybdenum, and consisting of 80-90 wt.% Ni3Al, 5-10 wt.% Ni and 2-10 wt.% Mo.

The task is also solved by a method for production of synthesis gas carbon dioxide conversion of methane using the inventive catalyst.

The resulting catalyst is highly active, stable, resistant to local overheating and thermal shocks, works with average contact times of 0.1-1 in one-step reaction of carbon dioxide methane conversion at 600-1000°C at atmospheric pressure.

A catalyst is a chemical combination of several metals and represents Internet lid, consisting of coarse particles or aggregates of particles.

The amount of Nickel and aluminum, it is necessary to obtain Ni3Al, chosen according to the phase diagram of the state. The number of input modifying additives of molybdenum, not more than 10 wt.% determine the impact on the microstructure of the active phase. Introduction more than 10 wt.% Mo leads to the coarsening of the structure of the active phase.

The catalytic system obtained by the method of self-propagating high temperature synthesis (SHS), carried out in modes of layer-by-layer combustion or thermal explosion, based on the use of internal chemical energy of the initial reagents and without some of the disadvantages of traditional methods of producing intermetallic compounds. He has a number of advantages - low power consumption, simplicity and single-stage process cycle of synthesis, expressnet, high performance, low-cost equipment, high purity product.

A method of producing a catalyst as proposed in the present invention, includes the drying of powders of the respective metals, dry mixing the components, forming the mass into the desired shape by a method of bilateral pressing, the initiation of combustion in a thin layer and directly burning, crushing and fractionation.

The invention provides a process katal the political conversion of light hydrocarbons, preferably methane, which allows to obtain a mixture of N2and with molar ratios of 0.5-1.5, mostly 1. As a source of raw materials can be used with natural gas.

The conversion is preferably carried out in one stage, with the use of intermetallic of aluminide Nickel modified Mo, in the temperature range 600-1000°C, preferably 950°C, at atmospheric pressure. When using methane to the desired volumetric ratio of CO2:CH4is 0.5-1.0, preferably 1. The reaction mixture containing methane (natural gas) and carbon dioxide, before entering the reactor is heated. During start-up and operation of the catalyst is controlled by the gas temperature at the inlet of the reactor, the temperature of the catalytic unit. The efficiency of the catalyst is characterized by the value of the degrees of conversion of methane and carbon dioxide, as well as the number of produced synthesis gas, expressed in volume percent. The composition of the initial reaction mixture and the reaction products are analyzed chromatographically.

The invention is illustrated by the following examples.

Example 1. To obtain catalyst Ni3Al+2%Mo take the powders of the metals Nickel (mark POE-1) weight 86 g aluminum (SDA-4) weight 12 g, molybdenum (OFS) by weight of 2 g, pre-dried in the tip is of 5 hours at a temperature of 150° With in argon. The powders are mixed and prepared the workpiece has a cylindrical shape by means of bilateral pressing on the press table with folding the mold and the floating piston. The porosity of 30-40%. SHS pressed samples is carried out in a bomb constant pressure the volume of 3 L. the Combustion is carried out in an argon atmosphere, the pressure is 0.1 MPa. To the end of injection molded preform down the heat pulse using a tungsten spiral, igniting the workpiece. In the surface layer is excited by a chemical reaction that spontaneously distributed in the form of a combustion wave traveling along the axis of the workpiece, leaving a cooling product. Obtained in the form of stabika the sample is then crushed and screened. The resulting material is a system consisting of Ni3Al, Ni and dispersed therein molybdenum (according to XRF).

For catalytic studies selected fraction with a particle size in the range 400-600 600-1000 microns and microns in quantities of 1 cm3placed in a tubular quartz reactor with an inner diameter of 5 mm Methane and carbon dioxide is passed through the catalyst in the temperature range 600-950°and a contact time of 0.6 C. the Process of methane conversion are in a fixed bed of catalyst at a pressure of 1 ATM. Gas chromatographic analysis of the gas about the W ill result, starting with the 600°and continue to 950°C. Regulate the volumetric rate of the source gas mixture, maintaining 100 ml/min Source components methane and carbon dioxide is supplied from the calculation of the molar ratio of the CO2:CH4=1:1. On the basis of chromatographic analysis in on-line calculate the conversion of methane and carbon dioxide and yields of the target products. The conversion of methane and carbon dioxide, as well as the yields of the target products of carbon monoxide and hydrogen for each composition shown in tables 1-3. Data on the stability of the catalyst are presented in table 4.

Example 2. To obtain catalyst Ni3Al+5% Mo take the powders of the metals Nickel (mark POE-1) weight 84 g aluminum (SDA-4) weight 11 grams of molybdenum by weight of 5, Then carry out the operations similar to example 1. Catalytic data are shown in table 2.

Example 3. To obtain catalyst Ni3Al+10% Mo take the powders of the metals Nickel (mark POE-1) weight 81 g aluminum (SDA-4) weighing 9 grams of molybdenum (OFS) weight of 10, Then use the procedure described in example 1. Catalytic data are shown in table 3.

Table 4 shows data on the stability of the catalyst Ni3Al+5% Mo. The stability of the inventive catalyst is higher than that of the prototype composition Ni3Al subjected to coking already after 16 hours. The catalysts containing molybdenum, ka is seen from tables 1-3, also shown increased catalytic activity compared to catalyst Ni3Al.

In the studied systems is formed synthesis gas composition H2:Approaching 1:1. By increasing the concentration of modifier in the system, the ratio of N2:WITH smoothly increases from 0.94 to Ni3Al+2% Mo, 1 to Ni3Al+5% Mo and 1.1 for Ni3Al+10% Mo.

Thus, the proposed catalyst in the process of conversion of methane exhibits a high catalytic activity and stability.

td align="center" namest="c6" nameend="c7"> 22
Table 1

Catalytic process data carbon dioxide methane conversion for catalyst Ni3Al+2% Mo
CatalystA, KConversion, %Exit (mol.) %
CO2CH4COH2
Ni3Al+2% Mo8730000
9730000
1073492515
112371423125
117387593934
122394744441
Table 2

Catalytic process data carbon dioxide methane conversion for catalyst Ni3Al+5% Mo
CatalystA, KConversion, %Exit (mol.)%
CO2CH4COH2
Ni3Al+5% Mo8730200
9730510
107344181912
1123835038 29
117397774146
122399894446

Table 3
Catalytic process data carbon dioxide methane conversion for catalyst
Ni3Al+10% Mo
Conversion, %Exit (mol.) %
CatalystA, K
CO2CH4COH2
8730000
9731 000
107338181711
Ni3Al+10% Mo
112356302617
117379493529
122395804146
Table 4

Data on the stability of the catalyst Ni3Al+5% Mo
CatalystTime, hConversion, %Exit (mol.) %
CO2CH4COH2
Ni3Al+5% Mo199894446
499894446
898884445
1298884345
2497874344
3696864243

1. Catalyst to produce synthesis gas carbon dioxide conversion of methane, characterized by the fact that he received samariterstrasse high-temperature synthesis and contains a matrix of aluminide Nickel, in which the dispersed Nickel and molybdenum, in the following ratio, wt.%:

Ni3Al80-90
Ni5-10
Mo2-10.

2. Method for production of synthesis gas placil is based conversion of methane using a catalyst, containing matrix aluminide Nickel, in which the dispersed Nickel, wherein the process is carried out in the presence of a catalyst according to claim 1.



 

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FIELD: chemistry.

SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.

EFFECT: high-grade purification of oil products from sulfur.

1 cl, 1 tbl, 2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention claims method of preparation of catalytic composition applied onto a carrier and acceptable for ethane and/or ethylene oxidation to acetic acid, where catalytic composition applied onto carrier includes catalyst of one or more metal components, on a carrier with aluminium alpha-oxide. Method involves the following stages: (a) preparation of suspension of one or more metal components and aluminium alpha-oxide carrier or carrier precedent particles, (b) dispersion drying of suspension, and optionally (c) calcination of dispersion-dried suspension to obtain catalytic composition applied onto carrier. Invention also claims catalytic composition applied onto carrier and obtained by the claimed method, and method of selective ethane and/or ethylene oxidation to acetic acid using the catalytic composition applied onto carrier.

EFFECT: high selectivity of target products and reduced COX generation.

44 cl, 2 tbl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention refers to oil fraction hydroprocessing catalyst. Oil fraction hydroprocessing catalyst contains insertion metal hydride based on alloy including metal of VIII group and lanthanide with catalyst having response surface and monoatomic hydrogen thereon. Oil fraction hydroprocessing catalyst contains insertion metal hydride based on alloy including metal of VIII group and metal of II group with catalyst having response surface and monatomic hydrogen thereon. Oil fraction hydroprocessing catalyst contains: radio-frequency or microwave carrier/absorber; and catalytic active phase including insertion metal hydride. Catalytic active phase thereof retains and produces monatomic hydrogen form. Oil fraction hydroprocessing catalyst contains: metal hydride with response surface; radio-frequency or microwave carrier/absorber; monatomic hydrogen on response surface; and at least one hydroprocessing component, cracking component and their combinations. Besides oil fraction hydroprocessing catalyst includes catalyst combination under p.2, where insertion metal hydride is produced by reaction of hydrogen and metal alloy A2T, where general formula A2T represents: A2-xMxT1-yBy, where x=0.0-0.5; y=0.0-0.5; A=Mg; T = at least either Ni or Cu; M=La; B = at least either Fe or Co with catalyst under p. 1 in with insertion metal hydride is produced by reaction of hydrogen and metal alloy chosen from group including AT5 and A2T14B and their combinations, where general formula for AT5 represents A1-xMxT5-y-zByCz, where x=0.0-1.0; y=0.0-2.5; z=0.0-0.5; A=Mm (misch metal); T=Ni; M = at least either La, Pr, Nd or Ce; B=Co; C = at least either Mn, Al or Cr; and where general formula for catalyst A2T14B represents A2-xMxT14-yCyDzB, where x=0.0-2.0; y=0.0-14; z=0.0-3.0; A=Nd; T=Fe; M = at least either La, Pr or Ce; B=boron; C=Co; D = at least either Cr, Ni or Mn. Besides oil fraction hydroprocessing catalyst includes catalyst combination under p. 2, where metal hydride contains Mg(2.05) Ni(0.95) Cu(0.07) with catalyst under p.1 with metal hydride containing at least either Mm(1.1)Ni(4.22)CO(0.42)Al(0.15)Mn(0.15) and Nd(2.05)Dy(0.25)Fe(1.3)B(1.05), and their combinations.

EFFECT: production of new organic compound processing catalyst.

25 cl, 7 ex, 10 tbl, 13 dwg

FIELD: chemistry.

SUBSTANCE: this invention refers to processing method of catalyst hard material containing at least one zeolite. Described is production method of mould catalyst hard material applied as reaction catalyst containing at least one titanium silicalite and being, at least fractionally crystallised and including stages as follows: (I) at least fractional crystallisation of at least one hard material containing at least, one titanium silicalite from synthesis mixture for the synthesis, producing mixture (I) containing at least mentioned hard material and mother liquor; (II) release and/or concentration of hard material in mixture (I); (C) calcination of hard material produced at stage (II); (W) reduction of calcinated hard material produced at stage (II) into contact with liquid deionised water; (S) moulding of hard material produced at stage (II); (C') calcination of mould produced at stage (S); with release and/or concentration at stage (II) carried out by method from group including filtration, ultrafiltration, diafiltration, centrifugation, spray drying and spray granulation and hard material moulding at stage (S) carried out by method from group including ball milling, pressing, extrusion, sintering, burning and caking. Besides described is mould catalyst hard material, produced by method specified above, as well as application of mould catalyst hard material and catalyst hard material for epoxidation of at least one compound with at least one C-C-double bond with at least, with one hydroperoxide.

EFFECT: improvement of catalyst properties of hard materials containing titanium silicalite, especially concerning selectivity.

14 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention refers to oil refining and petrochemical industry, specifically to methods of effective low-polymeric hydrocarbon pyrolysis catalysts. Described is low-polymeric paraffin fraction pyrolysis catalyst containing pentacyl family zeolite with silica ratio SiO2/Al2O3=20-80, modifiers chromium and fluorine, and binding agent aluminium oxide specific for the fact that simultaneously chromium and fluorine modified pentacyl family zeolite is used as catalyst base in ratio as follows, wt %: zeolite 55 - 80; chrome oxide 1 - 6.75; hydrogen fluoride 1 - 5.8; binding agent (γ-Al2O3) - the rest.

EFFECT: lowered number of technological operations for production of effective pentacyl containing catalyst for pyrolysis of low-polymeric hydrocarbons, reducted hard-to-dispose catalyst sewage, higher running time of regeneration-free pentacyl containing the catalyst.

1 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention refers to high metal catalyst compositions, production and application thereof in hydrotreating, specifically in hydrodesulfurisation and hydrodenitrogenating. Described is carrier-free catalyst composition containing one or more metals of VIb group, one or more metals of VIII group and refractory oxide material which contains at least 50 wt % of oxide-based titanium dioxide. Described is production method of catalyst compositions implying that one or more compounds of metal of VIb group is combined with one or more compounds of metal of VIII group and with refractory oxide material containing titanium dioxide with proton liquid and optionally alkaline compound; and catalyst composition is recovered by following precipitation. Described is application of composition described above or produced by method described above, moulded and sulphided if necessary, in hydrotreating of hydrocarbon raw materials.

EFFECT: higher activity of catalyst composition.

15 cl, 8 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to versions of catalyst compositions for ammonolysis of an unsaturated hydrocarbon into an unsaturated nitrile and to the method of converting olefin using such a catalyst. In the first version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaKbCscCedCreCOfNigFeiBijMo12Ox. In this formula, A is Rb, Li or their mixture, a assumes values from 0 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In the second version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaLia'KbCscCedCreCofNigFeiBijMo12Ox. A is Rb, a assumes values from 0 to 1, a' assumes values from 0.01 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In these given versions, the catalyst does not contain manganese and zinc and is put onto a carrier, selected from a group containing silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The method of converting olefin into acrylonitrile, methacrylonitrile and their mixture involves reacting olefin with a gas, containing molecular oxygen or ammonia in vapour phase, in the presence of the above mentioned catalyst. The olefin used is propylene, isobutylene or their mixture.

EFFECT: invention allows for obtaining a catalyst with high activity and increases output of nitriles.

14 cl, 1 tbl, 3 ex

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