CN110237848A - Supported multi-metal component catalyst, its preparation method and application, and cycloalkane hydrogenolysis ring-opening method - Google Patents

Abstract

The invention relates to the field of catalyst preparation, and discloses a supported multi-metal component catalyst, its preparation method and application, and a ring-opening method for cycloalkane hydrogenolysis. The catalyst includes a carrier, and a hydrogenation active metal component loaded on the carrier. The hydrogen active metal component comprises a first metal component M1 selected from cobalt and/or nickel elements, _a second metal component _M2 selected from platinum and/or palladium elements, and a third metal component M selected from iridium elements ₃ ; and the catalyst satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2-20, (M ₂ /M ₃ ) _XRF =0.05-10 . The catalyst provided by the invention is particularly suitable for catalyzing the ring-opening reaction of cycloalkane hydrogenolysis at low temperature, and has significantly higher activity and selectivity for catalyzing the hydrogenolysis ring-opening reaction of cycloalkane at low temperature.

Description

Supported multi-metal component catalyst and its preparation method and application and cycloalkane hydrogen unraveling ring method

technical field

The invention relates to the field of catalyst preparation, in particular to a supported multi-metal component catalyst, its preparation method and application, and a method for using the catalyst to catalyze cycloalkane hydrogenolysis and ring opening.

Background technique

With the development of the world economy, the demand for diesel is increasing day by day. It is impossible to meet this demand by straight-run diesel oil alone, so secondary processed diesel oil such as catalytic cracking diesel oil and coking diesel oil needs to be transferred. These secondary processed diesel oils contain a large amount of sulfur, nitrogen and aromatics, among which sulfur and nitrogen can be removed by traditional sulfide catalysts, and the conversion and removal of aromatics is the main technical difficulty. Excessively high aromatics content in diesel will not only reduce the cetane number and oil quality, but also increase particulate emissions in diesel combustion exhaust. Generally, the cetane number of normal or short side chain alkanes in diesel components is the highest, the cetane number of long side chain cycloalkanes and aromatics is higher, and the cetane number of short side chains or non-side chain cycloalkanes and aromatics is Lowest cetane number. Therefore, the increase of the cetane number of diesel oil by the hydrogenation saturation process of aromatics is limited, and the ring-opening reaction is expected to further increase the cetane number of diesel oil. With the increasingly stringent environmental regulations on clean energy, dearomatization of diesel fuel has become the focus of research. Therefore, it is of great significance to realize the highly selective ring opening of naphthenes to improve the quality of diesel oil.

The cycloalkane ring-opening reaction can proceed through the following three mechanisms: free radical reaction mechanism, carbanion mechanism and 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 naphthenes (Journal of the American Chemical Society, 2014, 136, 9664-9676; Journal of Physical Chemistry C, 2014, 118 , 20948-20958). The ring-opening reaction of cycloalkane molecules is easier to proceed than the side-chain scission reaction due to the intra-ring tension of cycloalkane molecules, so metal-catalyzed hydrogenolysis reaction is an effective method to obtain high-yield ring-opening products.

WO/2002/007881 discloses a catalyst and process for ring-opening of naphthenes. The ring-opening reaction is realized by using an iridium catalyst supported on a composite carrier of alumina and acidic silica-alumina molecular sieve. Moreover, the catalyst was calcined and regenerated after being exposed to an oxygen atmosphere at 250°C, and its ring-opening activity did not decrease significantly.

CN200480043382.0 discloses a catalyst and a cycloalkane ring-opening method using the catalyst. The catalyst comprises a Group VIII metal component, a molecular sieve, a refractory inorganic oxide and optional modifier components. Molecular sieves include MAPSO, SAPO, UZM-8, and UZM-15, Group VIII metals include platinum, palladium, and rhodium, and inorganic oxides are preferably alumina.

CN200910013536.6 discloses a cycloalkane hydroconversion catalyst and its preparation method and application. The catalyst includes a carrier and an active metal Pt, the carrier is composed 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% by weight, and the content of the active metal Pt in the catalyst is 0.05-0.6% by weight. The catalyst is prepared by an impregnation method, and the obtained catalyst can be used for hydrogenation conversion of various raw materials containing cycloalkane.

CN201110102568.0 discloses a selective ring-opening reaction process for aromatic hydrocarbons, and the reaction is carried out in two series-connected reactors. The material enters the first reactor for deep desulfurization and denitrogenation reactions, and the sulfur and nitrogen are removed through the H ₂ S and NH ₃ separation device. When the sulfur content in the material is lower than 50ppm and the nitrogen content is lower than 10ppm, the material enters the second reactor for selective ring-opening reaction. The reactor has two reaction beds, the hydrogenation saturated isomerization reaction is carried out in the first reaction bed, and the selective ring-opening reaction is carried out in the second reaction bed. The first reactor uses a metal sulfide catalyst, and the second reactor is loaded with a noble metal/molecular sieve-alumina catalyst.

However, there is still room for improvement and improvement in the ring-opening activity and selectivity of cycloalkane hydrogenolysis of the catalysts disclosed above.

Contents of the invention

The object of the present invention is to provide a kind of supported multi-metal component catalyst with higher ring-opening activity and selectivity of cycloalkane hydrogenolysis ring-opening activity and its Preparation method and application and ring-opening method of cycloalkane hydrogenolysis.

The first aspect of the present invention provides a supported multi-metal component catalyst, the catalyst comprising a carrier, a hydrogenation active metal component supported on the carrier, the hydrogenation active metal component comprising cobalt and/or nickel The first metal component M ₁ of the element, the second metal component M ₂ selected from platinum and/or palladium elements and the third metal component M ₃ of iridium element; and the catalyst satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2-20, (M ₂ /M ₃ ) _XRF =0.05-10, wherein, [(M ₂ +M ₃ )/M ₁ ] _XPS 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 elements in the catalyst characterized by X-ray photoelectron spectroscopy, [(M ₂ +M ₃ )/ M ₁ ] _XRF 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 elements in the catalyst characterized by X-ray fluorescence spectrum, (M ₂ /M ₃ ) _XRF is The weight ratio of the second metal component to the third metal component in the catalyst characterized by X-ray fluorescence spectrum in terms of metal elements.

The second aspect of the present invention provides a preparation method of a supported multi-metal component catalyst, the preparation method comprising the following steps:

(1) impregnating the support with a solution of a compound containing the first metal component, and then reducing and activating the impregnated support to obtain a catalyst precursor containing the first metal component;

(2) introducing a second metal component and a third metal component onto the catalyst precursor containing the first metal component by impregnation under a reducing or inert atmosphere;

Wherein, 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 the supported multi-metal component catalyst prepared by the above preparation method.

The fourth aspect of the present invention provides the application of the above-mentioned supported multi-metal component catalyst in catalyzing the hydrogenolysis ring-opening reaction of naphthenes.

The fifth aspect of the present invention provides a cycloalkane hydrogenolysis ring-opening method, the method comprising: under catalytic cycloalkane hydrogenolysis ring-opening conditions, the raw material containing cycloalkane, hydrogen and catalyst contact, wherein, the catalyst is the above-mentioned supported multi-metal component catalyst.

Compared with the catalyst with the same metal content prepared in the prior art, the supported multi-metal component catalyst of the present invention has significantly higher catalytic ring-opening activity for cycloalkane hydrogenolysis, and has a lower cracking rate at the same time. In addition, the catalyst provided by the invention is particularly suitable for catalyzing the ring-opening reaction of cycloalkane hydrogenolysis at low temperature (220-250° C.), and has significantly higher low-temperature catalytic ring-opening activity and selectivity of cycloalkane hydrogenolysis. Specifically, using methylcyclopentane as a raw material, the hydrogenolysis ring-opening performance of the catalysts was compared; it was found that the catalyst R1 prepared according to the method of the present invention has a catalytic performance significantly better than that of the catalyst D1 prepared by the co-impregnation method at a reaction temperature of 230 ° C. performance, the conversion rate of methylcyclopentane increases from 21.5% to 52.3%, and the selectivity of linear alkanes increases from 22.6% to 54.8%; compared with the catalyst D2 without the second metal component, it is prepared by the method of the present invention The catalyst R1 also has more excellent catalytic performance, the conversion rate of methylcyclopentane is increased from 23.1% to 52.3%, and the selectivity of linear alkanes is increased from 40.8% to 54.8%.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the X-ray photoelectron spectrum figure of the Ir 4f of the catalyst R1 that the embodiment of the present invention 1 makes and the comparative catalyst D1 that comparative example 1 makes;

Fig. 2 is the X-ray photoelectron spectrum figure of the Pt 4f of the catalyst R1 that the embodiment of the present invention 1 makes and the comparison catalyst D1 that comparative example 1 makes;

Fig. 3 is the X-ray photoelectron spectrum diagram of Ni 2p of catalyst R1 prepared in Example 1 of the present invention and comparative catalyst D1 prepared in Comparative Example 1.

Detailed ways

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The first aspect of the present invention provides a supported multi-metal component catalyst, the catalyst comprising a carrier, a hydrogenation active metal component supported on the carrier, the hydrogenation active metal component comprising cobalt and/or nickel The first metal component M ₁ of the element, the second metal component M ₂ selected from platinum and/or palladium elements and the third metal component M ₃ of iridium element; and the catalyst satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2-20, (M ₂ /M ₃ ) _XRF =0.05-10, wherein, [(M ₂ +M ₃ )/M ₁ ] _XPS 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 elements in the catalyst characterized by X-ray photoelectron spectroscopy, [(M ₂ +M ₃ )/ M ₁ ] _XRF 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 elements in the catalyst characterized by X-ray fluorescence spectrum, (M ₂ /M ₃ ) _XRF is The weight ratio of the second metal component to the third metal component in the catalyst characterized by X-ray fluorescence spectrum in terms of metal elements.

In the present invention, [(M ₂ +M ₃ )/M ₁ ] _XPS refers to the sum of the second metal component and the third metal component in the catalyst characterized by X-ray photoelectron spectroscopy and the first metal component in terms of metal elements The weight ratio calculated is obtained by converting the peak area of the characteristic peak of the corresponding metal element. The measuring instrument of X-ray photoelectron spectroscopy is the ESCALab250 instrument of Thermo Scientific Company, and the measuring conditions are as follows: the excitation light source is a 150kW monochromator Al Kα X-ray, and the binding energy is corrected by the C 1s peak (284.8eV).

In the present invention, [(M ₂ +M ₃ )/M ₁ ] _XRF is the sum of the second metal component and the third metal component in the catalyst characterized by X-ray fluorescence spectrum and the first metal component in terms of metal elements The weight ratio of (M ₂ /M ₃ ) _XRF is the mass ratio of the second metal component to the third metal component of the catalyst characterized by X-ray fluorescence spectrum in terms of metal elements. Wherein the measuring instrument of X-ray fluorescence spectrum is Rigaku Electric Industry Co., Ltd. 3271 instrument, and the measuring conditions are: powder sample compression molding, rhodium target, laser voltage 50kV, laser current 50mA.

According to a preferred embodiment of the present invention, the catalyst satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2-8, and further preferably the catalyst satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF = 2.5-5.

According to a preferred embodiment of the present invention, the catalyst satisfies (M ₂ /M ₃ ) _XRF =0.05-1.5, preferably the catalyst satisfies (M ₂ /M ₃ ) _XRF =0.1-1, further preferably the catalyst satisfies (M ₂ /M ₃ ) _XRF = 0.6-0.7. The inventors of the present invention have found that the specific (M ₂ /M ₃ ) _XRF , that is, the weight ratio of the second metal component to the third metal component in the catalyst characterized by X-ray fluorescence spectroscopy, in terms of metal elements, makes the catalyst Catalyst performance is further improved.

The present invention uses X-ray photoelectron spectroscopy to characterize the surface atomic composition of the catalyst, uses X-ray fluorescence spectroscopy to characterize the average atomic composition of the catalyst, and finds that the second metal component _M2 and the _third metal component M3 of the catalyst are in the first metal component M ₁ is enriched on the surface; and the weight ratio of the three metal components in terms of metal elements satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2 -20 is preferably in the range of 2-8, more preferably 2.5-5, most preferably 3.9-5. The catalyst provided by the invention has more excellent activity and selectivity in catalyzing the ring-opening reaction of cycloalkane hydrogenolysis.

The difference between the catalyst provided by the invention and the prior art catalyst is not only the structural characteristics of the multimetal component, but also the type of the multimetal component. The first metal component must be cobalt and/or nickel elements, and the second metal group must be cobalt and/or nickel. The component must be platinum and/or palladium, and the third metal component must be iridium. Although platinum, palladium and iridium are all noble metals, the combination of platinum and/or palladium and iridium in the above structure can achieve higher activity and selectivity in catalytic cycloalkane hydrogenolysis ring opening at low temperature (220-250°C).

According to a preferred embodiment of the present invention, the second metal component M ₂ is platinum. The preferred embodiment of the present invention is more conducive to the synergistic effect of the second metal component and the third metal component, and is more conducive to improving the ring-opening activity and selectivity of catalytic cycloalkane hydrogenolysis.

According to the present invention, preferably, the carrier is selected from at least one of alumina, silica, titania, magnesia, zirconia, thorium oxide, beryllium oxide, clay, molecular sieve and activated carbon, more preferably silica, One or more of alumina, Y-Beta and silica-alumina. The support may also be one or more of the above-mentioned supports modified with one or more of phosphorus, silicon, fluorine, and boron. The above-mentioned modified carrier can be obtained commercially, or can be modified by existing methods.

According to the supported multi-metal component catalyst provided by the present invention, preferably, based on the total weight of the catalyst, the content of the carrier is 66-94% by weight, and the content of the first metal component is 5-30% by weight, The content of the second metal component is 0.01-2% by weight, and the content of the third metal component is 0.01-2% by weight; further preferably, based on the total weight of the catalyst, the content of the carrier is 73-91.9% by weight, The content of the first metal component is 8-25% by weight, the content of the second metal component is 0.05-1% by weight, and the content of the third metal component is 0.05-1% by weight; Based on the total weight, the content of the carrier is 79-91.7% by weight, the content of the first metal component is 8-20% by weight, the content of the second metal component is 0.1-0.5% by weight, the content of the third metal component 0.2-0.5% by weight.

The second method of the present invention provides a preparation method of a supported multi-metal component catalyst, the preparation method comprising the following steps:

(1) impregnating the support with a solution of a compound containing the first metal component, and then reducing and activating the impregnated support to obtain a catalyst precursor containing the first metal component;

(2) introducing a second metal component and a third metal component onto the catalyst precursor containing the first metal component by impregnation under a reducing or inert atmosphere;

Wherein, 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 step (1) also contains the compound of the noble metal active component, and in terms of metal elements, the noble metal active component and the second metal component and the third metal component The weight ratio of the sum of is not more than 0.6, preferably 0.1-0.5. By introducing part of the noble metal active component in step (1), it can facilitate the reduction and activation reaction in the subsequent step (1) and the loading of the second metal component and the third metal component in step (2). In view of the above considerations, the amount of the noble metal active component in step (1) is less than the total amount of the second metal component and the third metal component in step (2).

The compound of the noble metal active component may be at least one selected from nitrates, acetates, sulfates, basic carbonates and chlorides containing ruthenium, rhodium, palladium, iridium and platinum elements.

The present invention is not particularly limited to the impregnation method of step (1), which can be various methods known to those skilled in the art, for example, equal volume impregnation method, supersaturated impregnation method, preferably equal volume impregnation method, specifically, the The volume of the impregnating solution is calculated according to the water absorption of the carrier. Specifically, the impregnation conditions of step (1) include: the temperature may be 10-90° C., preferably 15-40° C., and the time may be 1-10 hours, preferably 2-6 hours.

According to the preparation method provided by the present invention, the compound of the first metal component described in step (1) can be nitrate, acetate, sulfate, basic carbonate and chlorine with cobalt and/or nickel as cations at least one of the compounds.

In the solution containing the compound of the first metal component, the concentration of the compound of the first metal component is preferably 50-2000 g/L, more preferably 80-1500 g/L in terms of the first metal component.

The selection of the carrier is as described above and will not be repeated here.

According to a specific embodiment of the present invention, the method further includes: drying and calcining the impregnated support obtained in step (1) in sequence, and then performing the reduction activation. The drying temperature can be 80-150°C. The temperature of calcination can be 220-600°C (preferably 350-500°C), and the time can be 1-6 hours (preferably 3-5 hours).

According to the preparation method provided by the present invention, step (1) reduction activation is preferably carried out in a pure hydrogen atmosphere, or a mixed gas atmosphere of hydrogen and an inert gas, such as a mixed gas atmosphere of hydrogen, nitrogen and/or argon, and the reduction Conditions for activation include: a temperature of 200-500°C, preferably 300-500°C, more preferably 350-400°C, and a time of 1-12 hours, preferably 1-5 hours, more preferably 2-4 hours. The reduction activation pressure can be normal pressure or pressurized, specifically, the pressure of hydrogen can be 0.1-4 MPa, preferably 0.1-2 MPa. The pressure in the present invention refers to absolute pressure.

According to the present invention, preferably, step (2) introduces the second metal component and the third metal component on the catalyst precursor containing the first metal component by impregnation method through at least one of the following methods kind to implement:

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) impregnating the catalyst precursor containing the first metal component with a solution containing a compound of the third metal component, drying, and then impregnating with a solution containing a compound of the second metal component.

That is, in the preparation method provided by the present invention, the second metal component and the third metal component can be introduced by the co-impregnation method, or can be introduced by the step-by-step impregnation method, regardless of whether the second metal component or the third metal component is introduced first. Components can achieve the purpose of the invention of the present invention, but in order to further improve the catalytic performance of the catalyst, it is preferred to introduce the second metal component and the third metal component by the step-by-step impregnation method, and first introduce the third metal component, and then A second metal component is introduced. Most preferably, step (2) introduces the second metal component and the third metal component onto the catalyst precursor containing the first metal component by the impregnation method in the following manner: The solution of the compound of the component impregnates the catalyst precursor containing the first metal component, drying (preferably carried out under vacuum conditions or under the protection of an inert gas or a reducing gas, preferably using the gas of the impregnating atmosphere in step (2) to blow dry The impregnated product is dried in the same way), and then impregnated with a solution containing a compound of the second metal component.

The present invention is not particularly limited to the impregnation conditions described in step (2) embodiment 1), 2) and 3), as long as a corresponding amount of the second metal component and the third metal component can be introduced, preferably Preferably, the impregnation conditions include: a temperature of 10-90°C, more preferably 15-40°C, and a time of 0.1-10 hours, preferably 0.5-2 hours. Equal volume impregnation or supersaturated impregnation can be used.

According to a specific embodiment of the present invention, the volume of the soaking liquid used in step (2) is 0.5-10 times, preferably 1-3 times, the volume of the soaking liquid used in step (1).

Embodiments of the present invention 1), 2) and 3), the compounds of the second metal component can be various soluble compounds of platinum and/or palladium, such as nitrates containing platinum and/or palladium, At least one of acetate, sulfate, basic carbonate and chloride; the compound of the third metal component can be various soluble compounds of iridium, such as iridium-containing nitrate, acetic acid At least one of salt, sulfate, basic carbonate and chloride, preferably iridium chloride.

Embodiment 1), 2) and 3) of the present invention contain the solution of the compound of the second metal component and/or the compound of the third metal component, with the second metal component and/or the third metal component In other words, the concentration of the compound of the second metal component and/or the compound of the third metal component is 0.2-100 g/L, more preferably 1-50 g/L.

The present invention also includes drying the impregnated product of embodiment 1), 2) and 3), in order to prevent the metal active components in the catalyst from being oxidized, the drying is preferably under vacuum or inert gas or reducing gas protection The impregnated product is preferably dried by using the gas blow-drying method of the impregnated atmosphere in step (2).

The reducing atmosphere in the step (2) of the present invention may be a mixture gas atmosphere of reducing gas and inert gas, or may be a pure reducing gas atmosphere. The reducing atmosphere can be provided by pure hydrogen, or a mixture of hydrogen and 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 amount of the second metal component and the third metal component is such that in the catalyst, in terms of metal elements, the weight ratio of the second metal component and the third metal component is 0.05-10 :1, more preferably 0.05-1.5:1, still more preferably 0.1-1:1, most preferably 0.6-0.7:1. The weights of the second metal component and the third metal component in terms of metal elements can be measured by XRF.

According to the present invention, the above-mentioned preparation method preferably further includes: cooling the catalyst precursor containing the first metal component to room temperature or the impregnation temperature required in step (2) under hydrogen or an inert atmosphere, and then introducing the second metal component by impregnation points and the third metal component.

According to the present invention, the above-mentioned preparation method preferably further includes: passing into the solid obtained in step (2) a mixed gas with a volume ratio of _O2 / _N2 of 0.05-1% for 0.5-4 hours to passivate the metal active components therein , to obtain a catalyst that can be stored directly in air.

According to a preferred embodiment of the present invention, the amount of the first metal component, the second metal component and the third metal component is such that based on the total weight of the catalyst, the content of the carrier is 66-94% by weight, the first The content of the metal component is 5-30% by weight, the content of the second metal component is 0.01-2% by weight, and the content of the third metal component is 0.01-2% by weight; preferably, the content of the carrier is 73-91.9 % by weight, the content of the first metal component is 8-25% by weight, the content of the second metal component is 0.05-1% by weight, and the content of the third metal component is 0.05-1% by weight; further preferably, the carrier The content of the first metal component is 79-91.7% by weight, the content of the first metal component is 8-20% by weight, the content of the second metal component is 0.1-0.5% by weight, and the content of the third metal component is 0.2-0.5% by weight .

Compared with the catalyst with the same metal content prepared in the prior art, the supported multi-metal component catalyst of the present invention has significantly higher catalytic ring-opening activity for cycloalkane hydrogenolysis, and has a lower cracking rate at the same time. The reason may be that the special structural multi-metal component catalyst formed by the special metal composition has more suitable active sites for cycloalkane hydrogenolysis ring opening. The surface atomic composition of the catalyst was characterized by X-ray photoelectron spectroscopy, and the average atomic composition of the catalyst was characterized by X-ray fluorescence spectroscopy. It was found that the second metal component _M2 and the _third metal component M3 in the catalyst were in the first metal component M ₁ surface enrichment; and the weight ratio of the three metal components in terms of metal elements satisfies [(M ₂ +M ₃ )/M ₁ ] _XPS /[(M ₂ +M ₃ )/M ₁ ] _XRF =2- 20 is preferably in the range of 2-8, more preferably 2.5-5. The catalyst provided by the invention has more excellent activity and selectivity in catalyzing the ring-opening reaction of cycloalkane hydrogenolysis.

The third aspect of the present invention provides the supported multi-metal component catalyst prepared by the above preparation method.

The fourth aspect of the present invention provides the application of the above-mentioned supported multi-metal component catalyst in catalyzing the hydrogenolysis ring-opening reaction of naphthenes.

The fifth aspect of the present invention provides a cycloalkane hydrogenolysis ring-opening method, the method comprising: under catalytic cycloalkane hydrogenolysis ring-opening conditions, the raw material containing cycloalkane, hydrogen and catalyst contact, wherein, the catalyst is the above-mentioned supported multi-metal component catalyst.

The catalyst of the present invention can be used to catalyze the hydrogenolysis ring-opening reaction of various raw materials containing naphthenes (preferably the mass content of aromatics is less than 15%, and the mass content of sulfur is less than 30ppm), for example, the raw materials containing naphthenes are model compounds of naphthenes, or contain Naphthenic gasoline fraction, kerosene fraction, or diesel fraction, etc.

The conditions of the contact reaction (i.e. hydrogen dissociation and ring-opening reaction) can be carried out with reference to the prior art, for example, the temperature is 180-450 ° C, preferably 220-400 ° C, the pressure is 1-18 MPa, preferably 2-12 MPa, and the hydrogen-oil volume ratio is 50 -10000:1 is preferably 50-5000:1, and the mass space velocity is 0.1-100 hours ^-1 , preferably 0.2-80 hours ^-1 . According to a preferred embodiment of the present invention, the catalytic cycloalkane hydrogenolysis and ring-opening conditions include: a temperature of 220-250°C. The inventors of the present invention found that at a lower temperature, the catalyst provided by the present invention has higher activity and selectivity for catalyzing the ring-opening reaction of cycloalkane hydrogenolysis than the catalyst provided by the prior art.

The device for the contact reaction can be carried out in any reactor sufficient to make the feedstock oil contact with the multi-metal component catalyst under hydrogenation reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a mobile bed reactor or ebullating bed reactor.

The following examples facilitate a better understanding of the present invention, but do not limit the present invention. In the following examples, the percentages mentioned are all mass percentages unless otherwise specified. In the following examples, the measuring instrument of X-ray photoelectron energy spectrum is the ESCALab250 type instrument of Thermo Scientific Company, and the measuring condition is: the excitation light source is the monochromator Al Kα X-ray of 150kW, and the binding energy adopts C 1s peak (284.8eV) correction; The measuring instrument of X-ray fluorescence spectrum is Rigaku Electric Industry Co., Ltd. 3271 instrument, and the measuring conditions are: powder sample compression molding, rhodium target, laser voltage 50kV, laser current 50mA. And for the sake of simplicity, only the corresponding spectra of Example 1 and Comparative Example 1 are provided, and the calculation results of other Examples and Comparative Examples are directly given.

In the following examples, the catalyst composition is based on the total weight of the catalyst, the mass percentage of the first metal component, the second metal component, and the third metal component, and the composition is calculated by the amount of feed.

Example 1

This example is used to illustrate the catalyst provided by the present invention and its preparation method.

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of nickel nitrate and iridium chloride impregnation solution containing 167 grams per liter of nickel and 2.22 grams per liter of iridium were prepared. Decant the impregnation solution onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier (Sasol amorphous silicon aluminum, average particle size 40-80 microns, the same below), stir well at 25°C and let it stand for 4 hours, then dry it at 120°C , calcined at 350°C for 4 hours, hydrogen reduction at 350°C for 4 hours, and the hydrogen pressure was 0.1 MPa. Reduce to room temperature after reduction, and add 48.6 milliliters of iridium chloride containing 2.96 grams per liter of iridium and 2.96 grams per liter of platinum and platinum dichlorotetraammine in 48.6 milliliters under a hydrogen atmosphere. Blow dry with hydrogen. Then passivate for 0.5 hours with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R1, its composition, XPS and XRF characterization results are shown in Table 1, and the X-ray photoelectron spectra are shown in Fig. 1, Fig. 2 and Fig. 3 . The surface atomic ratio [(M ₂ +M ₃ )/M ₁ ] _XPS was calculated according to the corresponding peak areas of electron binding energies of Ir 4f, Pt 4f and Ni 2p. The composition is based on the total weight of the catalyst, and the mass percentages of the first metal component, the second metal component and the third metal component.

Comparative example 1

This comparative example is used to illustrate a comparative catalyst and its preparation method.

A comparative catalyst D1 with the same metal components as catalyst R1 was prepared by the co-impregnation method.

According to the metal salt content required by the equal-volume impregnation method, 32.4 milliliters of nickel nitrate, iridium chloride and dichlorotetraammine platinum impregnation solution containing 167 grams per liter of nickel, 6.67 grams per liter of iridium and 4.44 grams per liter of platinum were prepared. . Decant the impregnating liquid onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier, stir well at 25°C, let stand for 4 hours, dry at 120°C, bake at 350°C for 4 hours, reduce with hydrogen at 350°C for 4 hours, hydrogen The pressure is 0.1 MPa. After reduction, cool down to room temperature, passivate with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5% for 0.5 hours, and store in a desiccator for future use. The obtained catalyst is denoted as D1, and its composition, XPS and XRF characterization results are shown in Table 1. The X-ray photoelectron spectra are shown in Figure 1, Figure 2, and Figure 3.

Comparative example 2

The catalyst was prepared according to the method of Example 1, except that the impregnating liquid used for the second impregnation did not contain platinum element, and a comparative catalyst D2 was obtained, and its composition, XPS and XRF characterization results are shown in Table 1.

Comparative example 3

Prepare the catalyst according to the method of Example 1, the difference is that the second metal and the third metal are directly loaded without hydrogen reduction after the first metal is loaded and dried and calcined to obtain a comparative catalyst D3, which is characterized by its composition, XPS and XRF The results are shown in Table 1.

Comparative example 4

The catalyst was prepared according to the method of Example 1, except that the impregnating solution used for the second impregnation did not contain iridium element, and a comparative catalyst D4 was obtained, and its composition, XPS and XRF characterization results are shown in Table 1.

Comparative example 5

Prepare the catalyst according to the method of Example 1, the difference is that in the impregnating solution used for the second impregnation, the total loading of metal elements is kept constant, and tetraammine platinum dichloride is replaced by iridium chloride to obtain a comparative catalyst D5, which The composition, XPS and XRF characterization results are shown in Table 1.

Comparative example 6

Prepare the catalyst according to the method of Example 1, the difference is that in the impregnating solution used for the second impregnation, the total loading of metal elements is kept constant, and tetraammine platinum dichloride is replaced by potassium chloride to obtain a comparative catalyst D6, which The composition, XPS and XRF characterization results are shown in Table 1.

Comparative example 7

The catalyst was prepared according to the method of Example 1, except that the impregnating liquid used for the first impregnation did not contain nickel element, and a comparative catalyst D7 was obtained, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 2

This example is used to illustrate the catalyst provided by the present invention and its preparation method.

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of nickel nitrate and iridium chloride impregnation solution containing 167 grams per liter of nickel and 2.22 grams per liter of iridium were prepared. The impregnating liquid is decanted to 40 grams of hydrogen type Y-Beta composite molecular sieves-alumina carrier (prepared according to the carrier D1 of Example 1 of CN101992120A, the following is the same), stir evenly at 25 ° C, after standing for 4 hours, through 110 ° C Drying, calcination at 500°C for 4 hours, hydrogen reduction at 350°C for 4 hours, hydrogen pressure at 0.1 MPa. Reduce to room temperature after reduction, and add 48.6 milliliters of iridium chloride containing 2.96 grams per liter of iridium and 2.96 grams per liter of platinum and platinum dichlorotetraammine in 48.6 milliliters under a hydrogen atmosphere. Blow dry with hydrogen. Then passivate for 0.5 hours with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R2, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 3

This example is used to illustrate the catalyst provided by the present invention and its preparation method.

According to the required metal salt content of equal-volume impregnation method, 32.4 milliliters of cobalt nitrate and iridium chloride impregnating solution containing 330 grams per liter of cobalt and 1.11 grams per liter of iridium were prepared. Decant the impregnation solution onto 40 grams of hydrogen-type Y-Beta composite molecular sieve-alumina carrier, stir well at 25°C, let stand for 4 hours, dry at 120°C, roast at 350°C for 4 hours, and reduce with hydrogen at 400°C for 4 hours hour, the hydrogen pressure is 0.1 MPa. After reduction, it was lowered to room temperature, and 48.6 milliliters of iridium chloride containing 1.48 grams per liter of iridium and 1.48 grams per liter of platinum and platinum dichlorotetraammine in 48.6 milliliters were added under a hydrogen atmosphere, and left to stand for 1 hour before using Blow dry with hydrogen. Then passivate with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.2% for 5 hours, and store in a desiccator for future use. The obtained catalyst is denoted as R3, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 4

This example is used to illustrate the catalyst provided by the present invention and its preparation method.

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of cobalt nitrate and iridium chloride impregnation solution containing 110 g/liter of cobalt and 1.11 g/liter of iridium were prepared. Decant the impregnating liquid onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier, stir evenly at 25°C and let stand for 4 hours, then dry at 120°C, bake at 350°C for 4 hours, reduce with hydrogen at 350°C for 4 hours, hydrogen pressure is 0.1 MPa. Cool down to room temperature after reduction, and add 48.6 ml of a mixed aqueous solution of iridium chloride and chloroplatinic acid containing 1.48 g/L iridium and 1.48 g/L platinum under a hydrogen atmosphere, let it stand for 1 hour, and then dry it with hydrogen gas . Then passivate for 2 hours with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R4, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 5

This example is used to illustrate the catalyst provided by the present invention and its preparation method.

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of nickel nitrate and dichlorotetraammine platinum impregnation solution containing 167 grams per liter of nickel and 2.22 grams per liter of platinum were prepared. Decant the impregnating liquid onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier, stir evenly at 25°C and let stand for 4 hours, then dry at 120°C, bake at 350°C for 4 hours, reduce with hydrogen at 350°C for 4 hours, hydrogen pressure is 0.1 MPa. Reduce to room temperature after reduction, and add 48.6 milliliters of iridium chloride containing 2.96 grams per liter of iridium and 2.96 grams per liter of platinum and platinum dichlorotetraammine in 48.6 milliliters under a hydrogen atmosphere. Blow dry with hydrogen. Then passivate for 1 hour with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R5, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 6

According to the method of Example 1, the difference is that in the impregnating solution used for the second impregnation, the total loading of metal elements is kept constant, and tetraammine platinum dichloride is replaced by tetraammine palladium dinitrate to obtain catalyst R6, which The composition, XPS and XRF characterization results are shown in Table 1.

Example 7

This example is used to illustrate the catalyst provided by the present invention and its preparation method. According to the method of Example 1, the difference is that the second metal component and the third metal component are introduced by first impregnating the third metal component, and then impregnating the second metal component, specifically:

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of nickel nitrate and iridium chloride impregnation solution containing 167 grams per liter of nickel and 2.22 grams per liter of iridium were prepared. Decant the impregnating liquid onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier, stir evenly at 25°C and let stand for 4 hours, then dry at 120°C, bake at 350°C for 4 hours, reduce with hydrogen at 350°C for 4 hours, hydrogen pressure is 0.1 MPa. After reduction, it was lowered to room temperature, and 48.6 ml of iridium chloride aqueous solution containing 2.96 g/L iridium was added under a hydrogen atmosphere, allowed to stand for 1 hour, and then dried with hydrogen. Then add 48.6 milliliters of an aqueous solution of dichlorotetraammineplatinum containing 2.96 grams per liter of platinum under a hydrogen atmosphere, let it stand for 1 hour, and then dry it with hydrogen. Then passivate for 0.5 hours with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R7, and its composition, XPS and XRF characterization results are shown in Table 1.

Example 8

This example is used to illustrate the catalyst provided by the present invention and its preparation method. According to the method of Example 1, the difference is that the second metal component and the third metal component are introduced by impregnating the second metal component first, and then impregnating the third metal component, specifically:

According to the required metal salt content of the equal volume impregnation method, 32.4 milliliters of nickel nitrate and iridium chloride impregnation solution containing 167 grams per liter of nickel and 2.22 grams per liter of iridium were prepared. Decant the impregnating liquid onto 40 grams of SiO ₂ -Al ₂ O ₃ carrier, stir evenly at 25°C and let stand for 4 hours, then dry at 120°C, bake at 350°C for 4 hours, reduce with hydrogen at 350°C for 4 hours, hydrogen pressure is 0.1 MPa. After reduction, it was lowered to room temperature, and 48.6 ml of an aqueous solution of dichlorotetraammineplatinum containing 2.96 g/L of platinum was added under a hydrogen atmosphere, allowed to stand for 1 hour, and then dried with hydrogen. Then add 48.6 milliliters of iridium chloride aqueous solution containing 2.96 g/L of iridium under a hydrogen atmosphere, let stand for 1 hour, and then blow dry with hydrogen. Then passivate for 0.5 hours with a mixed gas with a volume ratio of O ₂ /N ₂ of 0.5%, and store in a desiccator for future use. The obtained catalyst is denoted as R8, and its composition, XPS and XRF characterization results are shown in Table 1.

Test example 1

This test example is used to evaluate the catalytic hydrogenolysis and ring-opening results of the model compound methylcyclopentane by the catalysts provided in the above examples and comparative examples. The specific evaluation process is as follows:

The activity of the catalyst was evaluated on a continuous flow fixed-bed microreactor. The feedstock oil was the model compound methylcyclopentane. The loading amount of the catalyst was 0.5 g. The reaction conditions were: the pressure was 3.0 MPa, and the feedstock oil intake was 0.2 ml /min, the volume ratio of hydrogen to oil is 1000, and the temperature is 230°C. After 6 hours of reaction, samples are taken for online gas chromatography analysis. Before starting the reaction, it was reduced for 2 hours in a hydrogen atmosphere at 230° C., a hydrogen pressure of 3.0 MPa, and a flow rate of 200 ml/min. The reaction results are listed in Table 2.

Table 1

Table 2

Example number Catalyst number Methylcyclopentane conversion (%) Linear alkanes 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

As can be seen from the foregoing, the catalyst R1 prepared according to the method of the present invention has a significantly better catalytic performance than the catalyst D1 prepared by the co-impregnation method at a reaction temperature of 230° C. property); From the comparison of Example 1 and Comparative Example 2, Comparative Example 4, and Comparative Example 5, it is found that the catalytic performance of the catalyst that adopts platinum and iridium elements to cooperate is more excellent than that of the catalyst that uses platinum or iridium elements alone; by Example 1 Compared with Example 7, it is found that the catalyst prepared by introducing the third metal component first and then the second metal component has better catalytic performance.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (15)

1. a kind of more metal component catalyst of support type, which includes the hydrogenation activity gold of carrier, load on this carrier Belong to component, the hydrogenation active metal component includes the first metal component M selected from cobalt and/or nickel element₁, selected from platinum and/or Second metal component M of palladium element₂With the third metal component M for iridium₃；And the catalyst meets [(M₂+M₃)/M₁]_XPS/ [(M₂+M₃)/M₁]_XRF=2-20, (M₂/M₃)_XRF=0.05-10, wherein [(M₂+M₃)/M₁]_XPSIt is with x-ray photoelectron spectroscopy table The summation of the second metal component and third metal component and the first metal component are in the catalyst of sign with the weight of elemental metal Than [(M₂+M₃)/M₁]_XRFBe in the catalyst of X-ray fluorescence spectra characterization the second metal component and third metal component it is total With with the first metal component with the weight ratio of elemental metal, (M₂/M₃)_XRFIt is in the catalyst of X-ray fluorescence spectra characterization Second metal component and third metal component are with the weight ratio of elemental metal.

2. catalyst according to claim 1, wherein the catalyst meets [(M₂+M₃)/M₁]_XPS/[(M₂+M₃)/M₁]_XRF =2-8, the preferably catalyst meet [(M₂+M₃)/M₁]_XPS/[(M₂+M₃)/M₁]_XRF=2.5-5.

3. catalyst according to claim 1, wherein the catalyst meets (M₂/M₃)_XRF=0.05-1.5, preferably this urge Agent meets (M₂/M₃)_XRF=0.1-1.

4. catalyst described in any one of -3 according to claim 1, wherein the second metal component M₂For platinum element；

The carrier is selected from aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve At least one of with active carbon.

5. catalyst described in any one of -4 according to claim 1, wherein on the basis of the total weight of catalyst, carrier Content be 66-94 weight %, the content of the first metal component is 5-30 weight %, and the content of the second metal component is 0.01-2 Weight %, the content of third metal component are 0.01-2 weight %；Preferably,

On the basis of the total weight of catalyst, the content of carrier is 73-91.9 weight %, and the content of the first metal component is 8-25 Weight %, the content of the second metal component are 0.05-1 weight %, and the content of third metal component is 0.05-1 weight %；Into one It walks preferably,

On the basis of the total weight of catalyst, the content of carrier is 79-91.7 weight %, and the content of the first metal component is 8-20 Weight %, the content of the second metal component are 0.1-0.5 weight %, and the content of third metal component is 0.2-0.5 weight %.

6. a kind of preparation method of the more metal component catalyst of support type, the preparation method include the following steps:

(1) it is obtained with the solution impregnating carrier of the compound containing the first metal component then by the carrier reduction activation after dipping To the catalyst precarsor for containing the first metal component；

(2) under reduction or inert atmosphere, by introducing the on the catalyst precarsor containing the first metal component described in dipping normal direction Two metal components and third metal component；

Wherein, first metal component be cobalt and/or nickel element, second metal component be platinum and/or palladium element, it is described Third metal component is iridium.

7. preparation method according to claim 6, wherein the compound containing the first metal component is molten in step (1) Liquid is also containing the compound of noble metal active component, and with elemental metal, noble metal active component and the second metal component and The weight ratio of the summation of third metal component is no more than 0.6, preferably 0.1-0.5.

8. preparation method according to claim 6, wherein in step (1),

It is the nitrate of cation, acetate, sulfate, alkali that the compound of first metal component, which is selected from cobalt and/or nickel, At least one of formula carbonate and chloride；

Preferably, the carrier be selected from aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, At least one of molecular sieve and active carbon；

Preferably, it is 10-90 DEG C that the condition of dipping, which includes: temperature, and preferably 15-40 DEG C, the time is 1-10 hours, preferably 2- 6 hours.

9. preparation method according to claim 6, wherein this method further include: the load after the dipping for obtaining step (1) Body is first successively dried and roasts, and then carries out the reduction activation again；

Preferably, the reduction activation carries out in a hydrogen atmosphere, and the condition of the reduction activation includes: that temperature is 200-500 DEG C, the time is 1-12 hours.

10. the preparation method according to any one of claim 6-9, wherein step (2) is described to pass through dipping normal direction institute State introduced on the catalyst precarsor containing the first metal component the second metal component and third metal component by following manner come into Row:

It is dry with the solution dipping catalyst precarsor for containing the first metal component of the compound containing third metal component, Then it is impregnated with the solution of the compound containing the second metal component；

Preferably, the dosage of the second metal component and third metal component makes in catalyst, with elemental metal, the second metal Component and the weight ratio of third metal component are 0.05-10:1, further preferably 0.05-1.5:1, most preferably 0.1-1:1；

Preferably, step (2) further include: be cooled to the catalyst precarsor containing the first metal component under hydrogen or inert atmosphere Dipping temperature needed for room temperature or step (2) then introduces the second metal component and third metal component by infusion process.

11. the preparation method according to any one of claim 6-9, wherein this method further include: obtained to step (2) To solid be passed through O₂/N₂Volume ratio is gaseous mixture 0.5-4 hours of 0.05-1%, to be passivated metal active constituent therein, is obtained To the catalyst that can directly save in air.

12. the preparation method according to any one of claim 6-11, wherein the first metal component, the second metal group Point and the dosage of third metal component make on the basis of the total weight of catalyst, the content of carrier is 66-94 weight %, first The content of metal component is 5-30 weight %, and the content of the second metal component is 0.01-2 weight %, and third metal component contains Amount is 0.01-2 weight %；Preferably, the content of carrier is 73-91.9 weight %, and the content of the first metal component is 8-25 weight % is measured, the content of the second metal component is 0.05-1 weight %, and the content of third metal component is 0.05-1 weight %；Further Preferably, the content of carrier is 79-91.7 weight %, and the content of the first metal component is 8-20 weight %, the second metal component Content be 0.1-0.5 weight %, the content of third metal component is 0.2-0.5 weight %.

13. the more metal component catalyst of support type made from preparation method described in any one of claim 6-12.

14. the more metal component catalyst of support type described in any one of claim 1-5 and 13 are in catalysis cycloalkane hydrogenolysis Application in ring-opening reaction.

15. a kind of cycloalkane hydrogenolysis open-loop method, this method comprises: ring will be contained in the case where being catalyzed cycloalkane hydrogenolysis open loop condition Raw material, the hydrogen of alkane are contacted with catalyst, wherein the catalyst is described in any one of claim 1-5 and 13 The more metal component catalyst of support type；

Preferably, it is 180-450 DEG C preferably 220-400 DEG C further that the catalysis cycloalkane hydrogenolysis open loop condition, which includes: temperature, It is preferred that 220-250 DEG C, pressure is the preferred 2-12 megapascal of 1-18 megapascal, and hydrogen to oil volume ratio is the preferred 50-5000:1 of 50-10000:1, Mass space velocity is 0.1-100 hours^-1Preferably 0.2-80 hours^-1。