CN110237848B - Supported multi-metal component catalyst, preparation method and application thereof, and naphthenic hydrocarbon hydrogenolysis ring-opening method - Google Patents

Supported multi-metal component catalyst, preparation method and application thereof, and naphthenic hydrocarbon hydrogenolysis ring-opening method Download PDF

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CN110237848B
CN110237848B CN201810195391.5A CN201810195391A CN110237848B CN 110237848 B CN110237848 B CN 110237848B CN 201810195391 A CN201810195391 A CN 201810195391A CN 110237848 B CN110237848 B CN 110237848B
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metal component
catalyst
metal
component
weight
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CN110237848A (en
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董笑
徐柏庆
郑仁垟
郑爱国
李会峰
李明丰
夏国富
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

The invention relates to the field of catalyst preparation, and discloses a supported multi-metal component catalyst, a preparation method and application thereof, and a cycloparaffin hydrogenolysis ring-opening method1A second metal component M selected from platinum and/or palladium elements2And a third metal component M of iridium3(ii) a And the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2‑20，(M2/M3)XRF0.05-10. The catalyst provided by the invention is particularly suitable for catalyzing the ring opening reaction of the naphthenic hydrocarbon hydrogenolysis at low temperature, and has obviously higher ring opening activity and selectivity of the naphthenic hydrocarbon hydrogenolysis at low temperature.

Description

Supported multi-metal component catalyst, preparation method and application thereof, and naphthenic hydrocarbon hydrogenolysis ring-opening method
Technical Field
The invention relates to the field of catalyst preparation, in particular to a supported multi-metal component catalyst, a preparation method and application thereof, and a method for catalyzing ring opening of cycloalkane by hydrogenolysis by using the catalyst.
Background
With the development of the world economy, the demand of diesel oil is increasing. The demand cannot be met by straight-run diesel oil alone, so that secondary processing diesel oil such as catalytic cracking diesel oil, coking diesel oil and the like needs to be added. The secondary processing diesel oil contains a large amount of sulfur, nitrogen and aromatic hydrocarbon, wherein the sulfur and the nitrogen can be removed by using a traditional sulfide catalyst at present, and the conversion and the removal of the aromatic hydrocarbon are main technical difficulties. An excessively high aromatics content in diesel fuel not only reduces the cetane number and oil quality, but also increases particulate emissions in the diesel fuel combustion exhaust. Normally, the cetane number of normal or short side chain paraffins in the diesel component is highest, the cetane number of paraffins and aromatics with long side chains is higher, and the cetane number of naphthenes and aromatics with short side chains or without side chains is lowest. Therefore, the cetane number of diesel oil is increased only in a limited way by the hydrogenation saturation process of aromatic hydrocarbon, and the cetane number of diesel oil is hopefully increased by the ring-opening reaction. With the increasing severity of environmental regulations on clean energy, dearomatization upgrading of diesel fuels has become a focus of research. Therefore, the realization of the high-selectivity ring opening of the cyclanes has very important significance for improving the quality of the diesel oil.
The cycloalkane ring-opening reaction can proceed by three mechanisms: a radical reaction mechanism, a carbonium ion mechanism and a hydrogenolysis mechanism (Journal of Catalysis,2002,210, 137-148). In contrast, the metal-catalyzed hydrogenolysis mechanism has higher activity and selectivity for the selective ring opening reaction of cycloalkanes (Journal of the American Chemical Society,2014,136, 9664-20976; Journal of Physical Chemistry C,2014,118, 20948-20958). The ring opening reaction is easier to perform than the side chain scission reaction due to the ring internal tension of cycloalkane molecules, so the metal-catalyzed hydrogenolysis reaction is an effective method to obtain high yield of ring-opened product.
WO/2002/007881 discloses a catalyst and process for ring opening of cycloalkanes by using iridium catalysts supported on a composite support of alumina and an acidic aluminosilicate molecular sieve. Moreover, the catalyst is calcined and regenerated by exposing the catalyst to oxygen atmosphere at 250 ℃, and the ring-opening activity of the catalyst is not remarkably reduced.
CN200480043382.0 discloses a catalyst and a cycloalkane ring-opening process using the catalyst. The catalyst comprises a group VIII metal component, a molecular sieve, a refractory inorganic oxide, and optionally a modifier component. The molecular sieves include MAPSO, SAPO, UZM-8 and UZM-15, the group VIII metals include platinum, palladium and rhodium, and the inorganic oxide is preferably alumina.
CN200910013536.6 discloses a naphthenic hydrocarbon hydroconversion catalyst, a preparation method and application thereof. The catalyst comprises a carrier and active metal Pt, wherein the carrier consists of a hydrogen type Y-Beta composite molecular sieve and an inorganic refractory oxide, the content of the hydrogen type Y-Beta composite molecular sieve in the catalyst carrier is 10-90 wt%, and the content of the active metal Pt in the catalyst is 0.05-0.6 wt%. The catalyst is prepared by adopting an impregnation method, and the obtained catalyst can be used for the hydro-conversion of various raw materials containing cycloparaffin.
CN201110102568.0 discloses an aromatic selective ring-opening reaction process, wherein the reaction is carried out in two reactors connected in series. The material enters a first reactor for deep desulfurization and denitrification reaction and passes through H2S and NH3The separation unit removes sulfur and nitrogen. When the sulfur content in the material is lower than 50ppm and the nitrogen content is lower than 10ppm, the material enters a second reactor for selective ring-opening reaction. The reactor has two reaction beds, the first reaction bed is used for hydrogenation saturation isomerization reaction, and the second reaction bed is used for selective ring-opening reaction. The first reactor uses metal sulfide catalyst, and the second reactor is filled with noble metal/molecular sieve-alumina catalyst.
However, there is still room for improvement and improvement in the naphthene hydrogenolysis ring-opening activity and selectivity of the above-disclosed catalysts.
Disclosure of Invention
The invention aims to overcome the defect that the hydrogenolysis ring-opening activity and selectivity of cycloalkane are still low in the prior art, and provides a supported multi-metal component catalyst with high hydrogenolysis ring-opening activity and selectivity of cycloalkane, a preparation method and application thereof, and a hydrogenolysis ring-opening method of cycloalkane.
The invention provides a supported multi-metal component catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises a first metal component M selected from cobalt and/or nickel elements1A second metal component M selected from platinum and/or palladium elements2And a third metal component M of iridium3(ii) a And the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2-20，(M2/M3)XRF0.05 to 10, wherein [ (M)2+M3)/M1]XPSThe weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst, characterized by X-ray photoelectron spectroscopy, [ (M)2+M3)/M1]XRF(M) is the weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst characterized by X-ray fluorescence spectrum2/M3)XRFThe weight ratio of the second metal component to the third metal component in the catalyst is characterized by X-ray fluorescence spectrum in terms of metal element.
The second aspect of the present invention provides a method for preparing a supported multi-metal component catalyst, comprising the steps of:
(1) impregnating a carrier with a solution containing a compound of a first metal component, and then reducing and activating the impregnated carrier to obtain a catalyst precursor containing the first metal component;
(2) introducing a second metal component and a third metal component onto the first metal component-containing catalyst precursor by an impregnation method under a reducing or inert atmosphere;
the first metal component is cobalt and/or nickel element, the second metal component is platinum and/or palladium element, and the third metal component is iridium element.
The third aspect of the present invention provides a supported multimetallic component catalyst prepared by the above preparation method.
The invention also provides the application of the supported multi-metal component catalyst in catalyzing the ring opening reaction of the hydrogenolysis of the cycloalkane.
In a fifth aspect, the present invention provides a process for the hydrogenolysis ring opening of a cycloalkane, the process comprising: under the condition of catalyzing the ring opening of the hydrogenolysis of the cycloalkane, the raw material containing the cycloalkane and hydrogen are contacted with a catalyst, wherein the catalyst is the supported multi-metal component catalyst.
Compared with the catalyst with the same metal content prepared by the prior art, the supported multi-metal component catalyst has obviously higher catalytic activity for the hydrogenolysis ring opening of the cycloalkane and lower cracking rate. In addition, the catalyst provided by the invention is particularly suitable for catalyzing the ring opening reaction of the naphthene hydrogenolysis at low temperature (220-250 ℃), and has obviously higher ring opening activity and selectivity of the naphthene hydrogenolysis at low temperature. Specifically, methylcyclopentane is used as a raw material, and the hydrogenolysis ring-opening performance of the catalyst is compared; the result shows that the catalyst R1 prepared by the method has obviously better catalytic performance than the catalyst D1 prepared by the co-impregnation method at the reaction temperature of 230 ℃, the conversion rate of the methylcyclopentane is improved to 52.3% from 21.5%, and the selectivity of the linear alkane is improved to 54.8% from 22.6%; compared with the catalyst D2 without the second metal component, the catalyst R1 prepared by the method of the invention has more excellent catalytic performance, the conversion rate of the methylcyclopentane is improved from 23.1% to 52.3%, and the selectivity of the linear alkane is improved from 40.8% to 54.8%.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray photoelectron spectrum of Ir 4f for catalyst R1 prepared in inventive example 1 and comparative catalyst D1 prepared in comparative example 1;
FIG. 2 is an X-ray photoelectron spectrum of Pt 4f of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1;
FIG. 3 is an X-ray photoelectron spectrum of Ni 2p of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a supported multi-metal component catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises a first metal component M selected from cobalt and/or nickel elements1A second metal component M selected from platinum and/or palladium elements2And a third metal component M of iridium3(ii) a And the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2-20，(M2/M3)XRF0.05 to 10, wherein [ (M)2+M3)/M1]XPSThe weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst, characterized by X-ray photoelectron spectroscopy, [ (M)2+M3)/M1]XRFCharacterised by X-ray fluorescence spectroscopyThe weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst of (M)2/M3)XRFThe weight ratio of the second metal component to the third metal component in the catalyst is characterized by X-ray fluorescence spectrum in terms of metal element.
In the present invention, [ (M)2+M3)/M1]XPSThe weight ratio of the sum of the second metal component and the third metal component in the catalyst characterized by X-ray photoelectron spectroscopy to the first metal component in terms of metal elements is obtained by conversion of the peak area of the characteristic peak of the corresponding metal element. The measuring instrument for the X-ray photoelectron spectroscopy is an ESCALB 250 type instrument of Thermo Scientific company, and the measuring conditions are as follows: the excitation source was a 150kW monochromator Al K.alpha.X-ray, and the binding energy was corrected for the C1 s peak (284.8 eV).
In the present invention, [ (M)2+M3)/M1]XRF(M) is the weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst characterized by X-ray fluorescence spectrum2/M3)XRFThe mass ratio of the second metal component to the third metal component of the catalyst in terms of metal elements is characterized by X-ray fluorescence spectrum. Wherein the measuring instrument of the X-ray fluorescence spectrum is a 3271 instrument of Nippon science and Motor industry Co., Ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50 mA.
According to a preferred embodiment of the present invention, the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF2-8, it is further preferred that the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2.5-5。
According to a preferred embodiment of the present invention, the catalyst satisfies (M)2/M3)XRF0.05 to 1.5, the catalyst preferably satisfies (M)2/M3)XRFWhen the amount is 0.1 to 1, the catalyst is more preferably fullFoot (M)2/M3)XRF0.6-0.7. The inventors of the present invention found that (M) is specific2/M3)XRFNamely the weight ratio of the second metal component to the third metal component in terms of metal elements in the catalyst characterized by X-ray fluorescence spectrum, so that the catalyst performance of the catalyst is further improved.
The invention adopts X-ray photoelectron spectrum to represent the surface atomic composition of the catalyst, adopts X-ray fluorescence spectrum to represent the average atomic composition of the catalyst, and finds out the second metal component M of the catalyst2And a third metal component M3In the first metal component M1Surface enrichment; and the weight ratio of the trimetal component calculated by the metal element satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRFPreferably 2-20, more preferably 2-8, more preferably 2.5-5, most preferably 3.9-5. The catalyst provided by the invention has more excellent activity and selectivity for catalyzing the ring opening reaction of naphthenic hydrocarbon hydrogenolysis.
The catalyst provided by the invention is different from the catalyst in the prior art not only in the structural characteristics of the multi-metal components, but also in the types of the multi-metal components, wherein the first metal component must be cobalt and/or nickel elements, the second metal component must be platinum and/or palladium elements, and the third metal component must be iridium elements. Although platinum, palladium and iridium belong to noble metals, the platinum and/or palladium element and iridium are matched with the structure to obtain higher catalytic naphthene hydrogenolysis ring-opening activity and selectivity at low temperature (220-250 ℃).
According to a preferred embodiment of the present invention, the second metal component M2Is platinum element. The preferred embodiment of the invention is more beneficial to the synergistic action of the second metal component and the third metal component, and is more beneficial to improving the catalytic ring opening activity and selectivity of the hydrogenolysis of the cycloalkane.
According to the present invention, preferably, the carrier is selected from at least one of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves and activated carbon, and further preferably one or more of silica, alumina, Y-Beta and silica-alumina. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method.
According to the supported multi-metal component catalyst provided by the invention, preferably, the content of the carrier is 66-94 wt%, the content of the first metal component is 5-30 wt%, the content of the second metal component is 0.01-2 wt%, and the content of the third metal component is 0.01-2 wt% based on the total weight of the catalyst; further preferably, the content of the carrier is 73 to 91.9 wt%, the content of the first metal component is 8 to 25 wt%, the content of the second metal component is 0.05 to 1 wt%, and the content of the third metal component is 0.05 to 1 wt%, based on the total weight of the catalyst; still more preferably, the carrier is present in an amount of 79 to 91.7 wt%, the first metal component is present in an amount of 8 to 20 wt%, the second metal component is present in an amount of 0.1 to 0.5 wt%, and the third metal component is present in an amount of 0.2 to 0.5 wt%, based on the total weight of the catalyst.
The second method of the invention provides a preparation method of a supported multi-metal component catalyst, which comprises the following steps:
(1) impregnating a carrier with a solution containing a compound of a first metal component, and then reducing and activating the impregnated carrier to obtain a catalyst precursor containing the first metal component;
(2) introducing a second metal component and a third metal component onto the first metal component-containing catalyst precursor by an impregnation method under a reducing or inert atmosphere;
the first metal component is cobalt and/or nickel element, the second metal component is platinum and/or palladium element, and the third metal component is iridium element.
Preferably, the solution containing the compound of the first metal component in the step (1) further contains a compound of a noble metal active component, and the weight ratio of the noble metal active component to the sum of the second metal component and the third metal component is not more than 0.6, preferably 0.1 to 0.5, in terms of the metal element. By introducing part of the noble metal active component in step (1), the progress of the reduction activation reaction in the subsequent step (1) and the supporting of the second metal component and the third metal component in step (2) can be facilitated. In view of the above considerations, the amount of the noble metal active component used in step (1) is less than the total amount of the second metal component and the third metal component used in step (2).
The compound of the noble metal active component may be at least one selected from nitrates, acetates, sulfates, hydroxycarbonates and chlorides of ruthenium, rhodium, palladium, iridium, platinum-containing elements.
The impregnation method in step (1) of the present invention is not particularly limited, and may be various methods known to those skilled in the art, for example, an equal volume impregnation method, a supersaturated impregnation method, preferably an equal volume impregnation method, and specifically, the volume of the impregnation solution is calculated as the water absorption rate of the carrier. Specifically, the impregnation conditions in step (1) include: the temperature may be from 10 to 90 deg.C, preferably from 15 to 40 deg.C, and the time may be from 1 to 10 hours, preferably from 2 to 6 hours.
According to the preparation method provided by the invention, the compound of the first metal component in the step (1) can be at least one of nitrate, acetate, sulfate, basic carbonate and chloride taking cobalt and/or nickel as cations.
In the solution containing the compound of the first metal component, the concentration of the compound of the first metal component is preferably 50 to 2000 g/l, more preferably 80 to 1500 g/l, in terms of the first metal component.
The selection of the carrier is as described above and will not be described in detail here.
According to a specific embodiment of the present invention, the method further comprises: and (2) drying and roasting the impregnated carrier obtained in the step (1) in sequence, and then carrying out reduction activation. The drying temperature may be 80-150 ℃. The temperature of the calcination may be 220-600 deg.C (preferably 350-500 deg.C), and the time may be 1-6 hours (preferably 3-5 hours).
According to the preparation method provided by the present invention, the reduction activation of step (1) is preferably performed in a pure hydrogen atmosphere, or a mixed gas atmosphere of hydrogen and an inert gas, such as a mixed gas atmosphere of hydrogen and nitrogen and/or argon, and the conditions of the reduction activation include: the temperature is 200-500 ℃, preferably 300-500 ℃, more preferably 350-400 ℃ and the time is 1-12 hours, preferably 1-5 hours, more preferably 2-4 hours. The pressure of the reduction activation may be either normal pressure or elevated pressure, and specifically, the pressure of hydrogen may be 0.1 to 4 MPa, preferably 0.1 to 2 MPa. The pressure in the present invention means an absolute pressure.
According to the present invention, preferably, the step (2) of introducing the second metal component and the third metal component onto the first metal component-containing catalyst precursor by an impregnation method is performed by at least one of the following means:
1) impregnating the catalyst precursor containing the first metal component with a solution containing a compound of the second metal component and a compound of the third metal component;
2) impregnating the catalyst precursor containing the first metal component with a solution containing a compound of the second metal component, drying, and then impregnating with a solution containing a compound of the third metal component;
3) the catalyst precursor containing the first metal component is impregnated with a solution containing a compound of the third metal component, dried, and then impregnated with a solution containing a compound of the second metal component.
That is, in the production method provided by the present invention, the second metal component and the third metal component may be introduced by a co-impregnation method, or may be introduced by a stepwise impregnation method, and the object of the present invention can be achieved regardless of whether the second metal component or the third metal component is introduced first, but in order to further improve the catalytic performance of the catalyst, it is preferable to introduce the second metal component and the third metal component by a stepwise impregnation method, and introduce the third metal component first, and then introduce the second metal component. Most preferably, the step (2) of introducing the second metal component and the third metal component onto the first metal component-containing catalyst precursor by impregnation is carried out by: impregnating the catalyst precursor containing the first metal component with a solution containing a compound of the third metal component, drying (preferably under vacuum conditions or under protection of an inert gas or a reducing gas, preferably by blow-drying using the gas atmosphere of the impregnation in step (2)), and then impregnating with a solution containing a compound of the second metal component.
The present invention does not particularly limit the conditions for the impregnation described in step (2) embodiments 1), 2) and 3), as long as the respective amounts of the second metal component and the third metal component can be introduced, and preferably, the impregnation conditions include: the temperature is 10 to 90 ℃, more preferably 15 to 40 ℃, and the time is 0.1 to 10 hours, preferably 0.5 to 2 hours. An equal volume impregnation or a supersaturation impregnation method may be used.
According to one embodiment of the invention, the volume of the impregnation solution used in step (2) is 0.5 to 10 times, preferably 1 to 3 times the volume of the impregnation solution used in step (1).
In embodiments 1), 2) and 3) of the present invention, each of the compounds of the second metal component may be various soluble compounds of platinum and/or palladium, for example, at least one of nitrate, acetate, sulfate, basic carbonate and chloride containing platinum and/or palladium; the compound of the third metal component may be various soluble compounds of iridium, for example, at least one of nitrate, acetate, sulfate, hydroxycarbonate and chloride containing iridium, preferably iridium chloride.
In the solutions containing the compound of the second metal component and/or the compound of the third metal component according to embodiments 1), 2), and 3) of the present invention, the concentration of the compound of the second metal component and/or the compound of the third metal component is 0.2 to 100 g/l, and more preferably 1 to 50 g/l, in terms of the second metal component and/or the third metal component.
The invention also comprises drying the products after the impregnation in the embodiments 1), 2) and 3), wherein the drying is preferably performed under vacuum condition or under the protection of inert gas or reducing gas in order to prevent the metal active components in the catalyst from being oxidized, and the drying is preferably performed by using a gas blow-drying mode of the impregnation atmosphere in the step (2).
The reducing atmosphere in step (2) of the present invention may be a mixed gas atmosphere of a reducing gas and an inert gas, or may be a pure reducing gas atmosphere. The reducing atmosphere may be provided by pure hydrogen or a mixture of hydrogen and an inert gas. The inert atmosphere is provided by an inert gas. The inert gas includes, but is not limited to, nitrogen and/or argon.
According to a preferred embodiment of the present invention, the second metal component and the third metal component are used in such amounts that the weight ratio of the second metal component to the third metal component in the catalyst, calculated as the metal element, is from 0.05 to 10: 1, more preferably 0.05 to 1.5: 1, more preferably 0.1 to 1: 1 is most preferably 0.6 to 0.7: 1. the weight of the second metal component and the third metal component in terms of metal element can be measured by XRF.
According to the present invention, the above preparation method preferably further comprises: the catalyst precursor containing the first metal component is cooled to room temperature or the impregnation temperature required in step (2) under hydrogen or an inert atmosphere, and then the second metal component and the third metal component are introduced by an impregnation method.
According to the present invention, the above preparation method preferably further comprises: introducing O into the solid obtained in the step (2)2/N2The mixed gas with the volume ratio of 0.05-1% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
According to a preferred embodiment of the present invention, the first metal component, the second metal component and the third metal component are used in such amounts that the content of the carrier is 66 to 94% by weight, the content of the first metal component is 5 to 30% by weight, the content of the second metal component is 0.01 to 2% by weight and the content of the third metal component is 0.01 to 2% by weight, based on the total weight of the catalyst; preferably, the content of the carrier is 73 to 91.9 wt%, the content of the first metal component is 8 to 25 wt%, the content of the second metal component is 0.05 to 1 wt%, and the content of the third metal component is 0.05 to 1 wt%; further preferably, the content of the carrier is 79 to 91.7 wt%, the content of the first metal component is 8 to 20 wt%, the content of the second metal component is 0.1 to 0.5 wt%, and the content of the third metal component is 0.2 to 0.5 wt%.
Compared with the catalyst with the same metal content prepared by the prior art, the supported multi-metal component catalyst has obviously higher catalytic activity for the hydrogenolysis ring opening of the cycloalkane and lower cracking rate. The reason for this is that the multi-metal component catalyst with special structure formed by special metal composition has more suitable naphthenic hydrocarbon hydrogenolysis ring opening active site. The surface atomic composition of the catalyst is represented by adopting X-ray photoelectron spectroscopy, the average atomic composition of the catalyst is represented by adopting X-ray fluorescence spectroscopy, and a second metal component M in the catalyst is found2And a third metal component M3In the first metal component M1Surface enrichment; and the weight ratio of the trimetal component calculated by the metal element satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRFPreferably 2-20, more preferably 2-8, and even more preferably 2.5-5. The catalyst provided by the invention has more excellent activity and selectivity for catalyzing the ring opening reaction of naphthenic hydrocarbon hydrogenolysis.
The third aspect of the present invention provides a supported multimetallic component catalyst prepared by the above preparation method.
The invention provides the application of the supported multi-metal component catalyst in catalyzing the ring opening reaction of the hydrogenolysis of the cycloalkane.
In a fifth aspect, the present invention provides a process for the hydrogenolysis ring opening of a cycloalkane, the process comprising: under the condition of catalyzing the ring opening of the hydrogenolysis of the cycloalkane, the raw material containing the cycloalkane and hydrogen are contacted with a catalyst, wherein the catalyst is the supported multi-metal component catalyst.
The catalyst of the invention can be used for catalyzing hydrogenolysis ring-opening reaction (preferably, the aromatic hydrocarbon content is less than 15% by mass, and the sulfur content is less than 30ppm by mass) of various raw materials containing naphthenes, such as naphthene model compounds, or gasoline fractions, kerosene fractions, diesel fractions and the like containing naphthenes.
The conditions of the contact reaction, i.e.the hydrogenolysis ring-opening reaction, can be carried out with reference to the prior art, for example at a temperature of 180 ℃ and 450 ℃ and preferably 220 DEG-400 ℃, pressure of 1-18 mpa, preferably 2-12 mpa, hydrogen to oil volume ratio of 50-10000: 1 preferably from 50 to 5000: 1, the mass space velocity is 0.1-100 hours-1Preferably 0.2 to 80 hours-1. According to a preferred embodiment of the invention, the catalytic cycloalkane hydrogenolysis ring opening conditions comprise: the temperature is 220 ℃ and 250 ℃. The invention has found that at lower temperature, the catalyst provided by the invention has higher activity and selectivity for catalyzing the ring opening reaction of naphthenic hydrocarbon hydrogenolysis than the catalyst provided by the prior art.
The means for the contact reaction may be carried out in any reactor sufficient for the contact reaction of the feedstock oil with the multimetallic component catalyst under hydrogenation reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor, or an ebullating bed reactor.
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. In the following examples, the percentages are by weight unless otherwise specified. In the following examples, the measuring instrument for X-ray photoelectron spectroscopy is an ESCALab250 type instrument from Thermo Scientific, under the following measurement conditions: an excitation light source is a monochromator Al K alpha X ray of 150kW, and the combination energy is corrected by adopting a C1 s peak (284.8 eV); the measuring instrument for X-ray fluorescence spectrum is 3271 type instrument of Nippon science and Motor industry Co., Ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50 mA. And for the sake of simplicity, only the corresponding spectra of example 1 and comparative example 1 are provided, and the other examples and comparative examples directly give the calculation results.
In the following examples, the catalyst composition is calculated by taking the total weight of the catalyst as a reference, and the mass percentages of the first metal component, the second metal component and the third metal component are calculated.
Example 1
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L iridium nitrate and iridium chloride is prepared.The impregnation solution was decanted to 40 g SiO2-Al2O3A carrier (Sasol amorphous silicon-aluminum, the average grain size is 40-80 microns, the same is shown below), evenly stirred and stood for 4 hours at 25 ℃, dried at 120 ℃, roasted for 4 hours at 350 ℃, reduced for 4 hours by hydrogen at 350 ℃, and the hydrogen pressure is 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution containing 2.96 g/l of iridium and 2.96 g/l of platinum, namely iridium chloride and tetraammineplatinum dichloride is added under the atmosphere of hydrogen, the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The obtained catalyst is marked as R1, and the composition, XPS and XRF characterization results are shown in Table 1, wherein X-ray photoelectron spectra are shown in figures 1, 2 and 3. Calculating according to the corresponding peak areas of the electron binding energies of Ir 4f, Pt 4f and Ni 2p to obtain the surface atomic ratio [ (M)2+M3)/M1]XPS. The composition is based on the total weight of the catalyst, and the mass percentage of the first metal component, the second metal component and the third metal component is used as the standard.
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a process for its preparation.
Comparative catalyst D1, which had the same metal composition as catalyst R1, was prepared according to a co-impregnation method.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L of nickel, 6.67 g/L of iridium and 4.44 g/L of platinum, nickel nitrate, iridium chloride and tetraammineplatinum dichloride is prepared. The impregnation solution was decanted to 40 g SiO2-Al2O3The carrier is stirred evenly at 25 ℃, is dried at 120 ℃ after being kept stand for 4 hours, is roasted at 350 ℃ for 4 hours, and is reduced by hydrogen at 350 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. Reducing, cooling to room temperature, and treating with O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as D1 and its composition, XPS and XRF characterization results are given in Table 1. Wherein the X-ray photoelectron spectrum is shown in figure 1, figure 2 and figure 3.
Comparative example 2
A catalyst was prepared as in example 1 except that the impregnation solution used in the second impregnation contained no platinum element, giving comparative catalyst D2 whose composition, XPS and XRF characterization results are given in Table 1.
Comparative example 3
A catalyst was prepared by following the procedure of example 1 except that the supporting of the second metal and the third metal was directly performed without hydrogen reduction after the first metal was supported and dried and calcined, to obtain comparative catalyst D3, whose composition, XPS and XRF characterization results are shown in Table 1.
Comparative example 4
A catalyst was prepared as in example 1 except that the impregnation solution used in the second impregnation contained no iridium to give comparative catalyst D4, the composition, XPS and XRF characterization of which are given in Table 1.
Comparative example 5
A catalyst was prepared as in example 1, except that the total loading of metal elements in the impregnation solution used in the second impregnation was kept constant and the platinum tetraammine dichloride was replaced by iridium chloride to give comparative catalyst D5, the composition, XPS and XRF characterization of which are given in Table 1.
Comparative example 6
A catalyst was prepared as in example 1, except that the total loading of metal elements in the impregnation solution used in the second impregnation was kept constant and the tetraammineplatinum dichloride was replaced by potassium chloride to give comparative catalyst D6, the composition, XPS and XRF characterization of which is shown in Table 1.
Comparative example 7
A catalyst was prepared as in example 1 except that the impregnation solution used in the first impregnation contained no nickel, resulting in comparative catalyst D7, the composition, XPS and XRF characterization of which are shown in Table 1.
Example 2
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L iridium nitrate and iridium chloride is prepared. The impregnation liquor was decanted to 40 g of a hydrogen-type Y-Beta composite molecular sieve-alumina support (according to C)N101992120A prepared as described below for carrier D1 of example 1), stirred at 25 ℃, left to stand for 4 hours, oven dried at 110 ℃, calcined at 500 ℃ for 4 hours, and reduced with hydrogen at 350 ℃ for 4 hours under a hydrogen pressure of 0.1 mpa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution containing 2.96 g/l of iridium and 2.96 g/l of platinum, namely iridium chloride and tetraammineplatinum dichloride is added under the atmosphere of hydrogen, the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as R2 and its composition, XPS and XRF characterization results are given in Table 1.
Example 3
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by the equal-volume impregnation method, 32.4 ml of cobalt nitrate and iridium chloride impregnation solution containing 330 g/l of cobalt and 1.11 g/l of iridium is prepared. Decanting the maceration extract to 40 g hydrogen type Y-Beta composite molecular sieve-alumina carrier, stirring at 25 deg.C, standing for 4 hr, oven drying at 120 deg.C, calcining at 350 deg.C for 4 hr, and reducing with 400 deg.C hydrogen for 4 hr under 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution containing 1.48 g/L of iridium and 1.48 g/L of platinum, namely iridium chloride and tetraammineplatinum dichloride is added under the atmosphere of hydrogen, the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.2% for 5 hours, and storing in a dryer for standby. The catalyst obtained was designated as R3 and its composition, XPS and XRF characterization results are given in Table 1.
Example 4
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by the equal-volume impregnation method, 32.4 ml of cobalt nitrate and iridium chloride impregnation solution containing 110 g/l of cobalt and 1.11 g/l of iridium is prepared. The impregnation solution was decanted to 40 g SiO2-Al2O3The carrier is evenly stirred and kept stand for 4 hours at 25 ℃, then is dried at 120 ℃, is roasted for 4 hours at 350 ℃, and is reduced by hydrogen at 350 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. Reducing to room temperature after reduction, and introducing hydrogen48.6 ml of mixed aqueous solution of iridium chloride and chloroplatinic acid containing 1.48 g/l of iridium and 1.48 g/l of platinum is added under the atmosphere, and the mixture is kept stand for 1 hour and dried by hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 2 hours, and storing the gas in a dryer for standby. The catalyst obtained was designated as R4 and its composition, XPS and XRF characterization results are given in Table 1.
Example 5
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by the equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L platinum and containing nickel nitrate and platinum tetraammine dichloride is prepared. The impregnation solution was decanted to 40 g SiO2-Al2O3The carrier is evenly stirred and kept stand for 4 hours at 25 ℃, then is dried at 120 ℃, is roasted for 4 hours at 350 ℃, and is reduced by hydrogen at 350 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution containing 2.96 g/l of iridium and 2.96 g/l of platinum, namely iridium chloride and tetraammineplatinum dichloride is added under the atmosphere of hydrogen, the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 1 hour, and storing the gas in a dryer for standby. The catalyst obtained was designated as R5 and its composition, XPS and XRF characterization results are given in Table 1.
Example 6
Catalyst R6 was prepared according to the procedure in example 1, except that the total loading of metal elements in the impregnation solution used in the second impregnation was kept constant, and tetraammineplatinum dichloride was replaced by tetraamminepalladium dinitrate, the composition, XPS and XRF characterization results of which are shown in Table 1.
Example 7
This example serves to illustrate the catalysts and the process for their preparation according to the invention. The process of example 1 is followed except that the second metal component and the third metal component are introduced by impregnating the third metal component first and then the second metal component, specifically:
according to the content of metal salt required by the equal-volume impregnation method, 32.4 ml of impregnation containing 167 g/L nickel and 2.22 g/L iridium of nickel nitrate and iridium chloride is preparedAnd (4) soaking the solution. The impregnation solution was decanted to 40 g SiO2-Al2O3The carrier is evenly stirred and kept stand for 4 hours at 25 ℃, then is dried at 120 ℃, is roasted for 4 hours at 350 ℃, and is reduced by hydrogen at 350 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of iridium chloride aqueous solution containing 2.96 g/L of iridium is added under the atmosphere of hydrogen, and the mixture is kept stand for 1 hour and then dried by hydrogen. Then 48.6 ml of an aqueous solution containing platinum (2.96 g/l) and tetraammineplatinum dichloride is added under the hydrogen atmosphere, and the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as R7 and its composition, XPS and XRF characterization results are given in Table 1.
Example 8
This example serves to illustrate the catalysts and the process for their preparation according to the invention. The process of example 1 is followed except that the second metal component and the third metal component are introduced by impregnating the second metal component first and then the third metal component, specifically:
according to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L iridium nitrate and iridium chloride is prepared. The impregnation solution was decanted to 40 g SiO2-Al2O3The carrier is evenly stirred and kept stand for 4 hours at 25 ℃, then is dried at 120 ℃, is roasted for 4 hours at 350 ℃, and is reduced by hydrogen at 350 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of aqueous solution containing platinum of 2.96 g/l tetraammineplatinum dichloride is added under the atmosphere of hydrogen, and the mixture is stood for 1 hour and then dried by hydrogen. Then 48.6 ml of iridium chloride aqueous solution containing 2.96 g/l of iridium is added under the condition of introducing hydrogen atmosphere, and the mixture is stood for 1 hour and then dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as R8 and its composition, XPS and XRF characterization results are given in Table 1.
Test example 1
This test example was used to evaluate the catalytic hydrogenolysis ring-opening results of the catalysts provided in the above examples and comparative examples on the model compound methylcyclopentane. The specific evaluation process is as follows:
the activity evaluation of the catalyst is carried out on a continuous flow fixed bed micro-reaction device, raw oil is a model compound methyl cyclopentane, the loading amount of the catalyst is 0.5 g, and the reaction conditions are as follows: the pressure is 3.0 MPa, the input amount of raw oil is 0.2 ml/min, the volume ratio of hydrogen to oil is 1000, the temperature is 230 ℃, and sampling is carried out on-line gas chromatographic analysis after 6 hours of reaction. Before the reaction, the reaction mixture was reduced at 230 ℃ under a hydrogen pressure of 3.0 MPa at a flow rate of 200 ml/min for 2 hours. The reaction results are shown in Table 2.
TABLE 1
Figure BDA0001592936000000181
Figure BDA0001592936000000191
TABLE 2
Example numbering Catalyst numbering Methylcyclopentane conversion (%) Straight chain alkane selectivity (%)
Example 1 R1 52.3 54.8
Comparative example 1 D1 21.5 22.6
Comparative example 2 D2 35.4 37.4
Comparative example 3 D3 23.1 21.7
Comparative example 4 D4 29.5 40.8
Comparative example 5 D5 49.3 29.8
Comparative example 6 D6 21.1 44.3
Comparative example 7 D7 32.9 34.7
Example 2 R2 51.2 53.7
Example 3 R3 46.1 52.3
Example 4 R4 43.5 52.9
Example 5 R5 52.2 52.9
Example 6 R6 48.9 51.2
Example 7 R7 53.4 56.5
Example 8 R8 50.1 50.6
From the above, it can be seen that the catalyst R1 prepared by the method of the invention has obviously better catalytic performance (the conversion rate of methylcyclopentane and the selectivity of straight-chain alkane) than the catalyst D1 prepared by the co-impregnation method at the reaction temperature of 230 ℃; from the comparison between example 1 and comparative example 2, comparative example 4 and comparative example 5, it was found that the catalyst using the combination of platinum and iridium is more excellent in catalytic performance than the catalyst using platinum or iridium alone; it is found by comparing example 1 with example 7 that the catalyst prepared by introducing the third metal component first and then the second metal component is more excellent in catalytic performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (33)

1. A supported multi-metal component catalyst is composed of a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises a first metal component M selected from cobalt and/or nickel elements1A second metal component M selected from platinum and/or palladium elements2And a third metal component M of iridium3(ii) a And the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2-20，(M2/M3)XRF0.05 to 10, wherein [ (M)2+M3)/M1]XPSThe weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst, characterized by X-ray photoelectron spectroscopy, [ (M)2+M3)/M1]XRF(M) is the weight ratio of the sum of the second metal component and the third metal component to the first metal component in terms of metal element in the catalyst characterized by X-ray fluorescence spectrum2/M3)XRFThe weight ratio of the second metal component to the third metal component in the catalyst is characterized by X-ray fluorescence spectrum in terms of metal element.
2. The method of claim 1A catalyst, wherein the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2-8。
3. The catalyst of claim 1, wherein the catalyst satisfies [ (M)2+M3)/M1]XPS/[(M2+M3)/M1]XRF＝2.5-5。
4. The catalyst of claim 1, wherein the catalyst satisfies (M)2/M3)XRF＝0.05-1.5。
5. The catalyst of claim 1, wherein the catalyst satisfies (M)2/M3)XRF＝0.1-1。
6. The catalyst according to any one of claims 1 to 5, wherein the second metal component M2Is platinum element;
the carrier is at least one selected from alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve and activated carbon.
7. The catalyst according to any one of claims 1 to 5, wherein the carrier is present in an amount of 66 to 94 wt%, the first metal component is present in an amount of 5 to 30 wt%, the second metal component is present in an amount of 0.01 to 2 wt%, and the third metal component is present in an amount of 0.01 to 2 wt%, based on the total weight of the catalyst.
8. The catalyst of any one of claims 1 to 5, wherein the support is present in an amount of 73 to 91.9 wt%, the first metal component is present in an amount of 8 to 25 wt%, the second metal component is present in an amount of 0.05 to 1 wt%, and the third metal component is present in an amount of 0.05 to 1 wt%, based on the total weight of the catalyst.
9. The catalyst of any one of claims 1 to 5, wherein the carrier is present in an amount of 79 to 91.7 wt%, the first metal component is present in an amount of 8 to 20 wt%, the second metal component is present in an amount of 0.1 to 0.5 wt%, and the third metal component is present in an amount of 0.2 to 0.5 wt%, based on the total weight of the catalyst.
10. A process for the preparation of a supported multimetallic component catalyst according to any one of claims 1 to 9, comprising the steps of:
(1) impregnating a carrier with a solution containing a compound of a first metal component, and then reducing and activating the impregnated carrier to obtain a catalyst precursor containing the first metal component;
(2) introducing a second metal component and a third metal component onto the first metal component-containing catalyst precursor by an impregnation method under a reducing or inert atmosphere;
the first metal component is cobalt and/or nickel element, the second metal component is platinum and/or palladium element, and the third metal component is iridium element.
11. The production method according to claim 10, wherein the solution containing the compound of the first metal component in the step (1) further contains a compound of a noble metal active component, and a weight ratio of the noble metal active component to the sum of the second metal component and the third metal component added in the step (2) is not more than 0.6 in terms of metal element.
12. The production method according to claim 10, wherein the solution containing the compound of the first metal component in the step (1) further contains a compound of a noble metal active component, and the weight ratio of the noble metal active component to the sum of the second metal component and the third metal component added in the step (2) is 0.1 to 0.5 in terms of metal element.
13. The production method according to claim 10, wherein, in the step (1),
the compound of the first metal component is selected from at least one of nitrate, acetate, sulfate, basic carbonate and chloride of which cobalt and/or nickel is a cation.
14. The production method according to claim 10, wherein in step (1), the support is selected from at least one of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, and activated carbon.
15. The production method according to claim 10, wherein in the step (1), the impregnation conditions include: the temperature is 10-90 ℃ and the time is 1-10 hours.
16. The production method according to claim 10, wherein in the step (1), the impregnation conditions include: the temperature is 15-40 deg.C, and the time is 2-6 hr.
17. The method of claim 10, further comprising: and (2) drying and roasting the impregnated carrier obtained in the step (1) in sequence, and then carrying out reduction activation.
18. The production method according to claim 17, wherein the reductive activation is performed under a hydrogen atmosphere, and the conditions of the reductive activation include: the temperature is 200 ℃ and 500 ℃ and the time is 1-12 hours.
19. The production method according to any one of claims 10 to 18, wherein the introducing of the second metal component and the third metal component onto the first metal component-containing catalyst precursor by the impregnation method in step (2) is performed by:
the catalyst precursor containing the first metal component is impregnated with a solution containing a compound of the third metal component, dried, and then impregnated with a solution containing a compound of the second metal component.
20. The production method according to any one of claims 10 to 18, wherein the second metal component and the third metal component are used in such amounts that the weight ratio of the second metal component to the third metal component in the catalyst, calculated as the metal element, is from 0.05 to 10: 1.
21. the production method according to any one of claims 10 to 18, wherein the second metal component and the third metal component are used in such amounts that the weight ratio of the second metal component to the third metal component in the catalyst, calculated as the metal element, is from 0.05 to 1.5: 1.
22. the production method according to any one of claims 10 to 18, wherein the second metal component and the third metal component are used in such amounts that the weight ratio of the second metal component to the third metal component in the catalyst, calculated as the metal element, is from 0.1 to 1: 1.
23. the production method according to any one of claims 10 to 18, wherein the step (2) further comprises: the catalyst precursor containing the first metal component is cooled to room temperature or the impregnation temperature required in step (2) under hydrogen or an inert atmosphere, and then the second metal component and the third metal component are introduced by an impregnation method.
24. The production method according to any one of claims 10 to 18, wherein the method further comprises: introducing O into the solid obtained in the step (2)2/N2The mixed gas with the volume ratio of 0.05-1% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
25. The production method according to any one of claims 10 to 18, wherein the first metal component, the second metal component and the third metal component are used in an amount such that the content of the support is from 66 to 94% by weight, the content of the first metal component is from 5 to 30% by weight, the content of the second metal component is from 0.01 to 2% by weight and the content of the third metal component is from 0.01 to 2% by weight, based on the total weight of the catalyst.
26. The production method according to any one of claims 10 to 18, wherein the first metal component, the second metal component and the third metal component are used in an amount such that the content of the support is 73 to 91.9% by weight, the content of the first metal component is 8 to 25% by weight, the content of the second metal component is 0.05 to 1% by weight and the content of the third metal component is 0.05 to 1% by weight, based on the total weight of the catalyst.
27. The production method according to any one of claims 10 to 18, wherein the first metal component, the second metal component and the third metal component are used in an amount such that the content of the support is 79 to 91.7% by weight, the content of the first metal component is 8 to 20% by weight, the content of the second metal component is 0.1 to 0.5% by weight and the content of the third metal component is 0.2 to 0.5% by weight, based on the total weight of the catalyst.
28. A supported multimetallic component catalyst made by the process of any one of claims 10 to 27.
29. Use of the supported multimetallic component catalyst of any one of claims 1 to 9 and 28 for catalyzing a cycloalkane hydrogenolysis ring opening reaction.
30. A process for the hydrogenolysis ring opening of a cycloalkane comprising: contacting a feedstock containing cycloalkanes, hydrogen and a catalyst under conditions to catalyze the hydrogenolysis ring opening of cycloalkanes, wherein the catalyst is a supported multimetallic component catalyst as described in any one of 1-9 and 28.
31. The method of claim 30, wherein the catalytic cycloalkane hydrogenolysis ring opening conditions comprise: the temperature is 180 ℃ and 450 ℃, the pressure is 1-18 MPa, and the volume ratio of hydrogen to oil is 50-10000: 1, the mass space velocity is 0.1-100 hours-1。
32. The method of claim 30, wherein the catalytic cycloalkane hydrogenolysis ring opening conditions comprise: the temperature is 220 ℃ and 400 ℃, the pressure is 2-12 MPa, the volume ratio of hydrogen to oil is 50-5000: 1, the mass space velocity is 0.2-80 hours-1。
33. The method of claim 30, wherein the catalytic cycloalkane hydrogenolysis ring opening conditions comprise: the temperature is 220 ℃ and 250 ℃.
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