A method for directly preparing higher alcohols from olefins and synthesis gas in one step

Abstract

The present invention relates to a method for directly preparing higher alcohols from olefins and synthesis gas in one step. The reaction uses olefins and synthesis gas as raw materials, and directly prepares higher alcohols in one step under the action of a composite catalyst. The composite catalyst is composed of an Rh-based multiphase catalyst as a first component and a Ni-based multiphase catalyst as a second component. The first component, the Rh-based multiphase catalyst, is composed of a metal component Rh and an organic ligand polymer, and the organic ligand polymer is a porous polymer generated by solvent thermal polymerization of an organic P ligand containing a vinyl group. The second component, the Ni-based multiphase catalyst, is composed of a main active component Ni, a metal auxiliary agent, a selectivity improver and a carrier. The reaction process of the method has a high raw material conversion rate and a target product yield, and effectively reduces the energy consumption of the reaction process. The present invention provides a new route for directly preparing higher alcohols from olefins and synthesis gas in one step, which has broad application prospects.

Description

Technical Field

[0001] The invention relates to a method for directly preparing higher alcohols from olefins and synthesis gas in one step, belonging to the technical field of heterogeneous catalysis. Background Art

[0002] Olefin hydroformylation is a reaction process in which olefins react with synthesis gas (mixed gas of CO and H2) under the action of transition metal complex catalysts to generate aldehydes or alcohols with one more carbon atom than the original olefins. The aldehydes, alcohols and their derivatives produced in this way are widely used as plasticizers, surfactants, solvents and fragrances. At present, more than 22 million tons of aldehydes and alcohols are produced annually worldwide using olefin hydroformylation technology. However, in most cases, the product aldehyde is often not the final product. The activity of the aldehyde group can be further converted into more valuable fine chemicals. For example, the olefin hydroformylation-reductive hydrogenation tandem reaction, which has the most industrial application value, can directly obtain the target product alcohol in a "one-pot" reaction. The olefin hydroformylation-reductive hydrogenation tandem reaction can avoid the separation and purification steps of intermediate products and effectively reduce the generation of by-products; at the same time, it can shorten the reaction process and effectively reduce the reaction energy consumption, thereby achieving efficient and economical synthetic alcohol products.

[0003] At present, there are many research reports on olefin hydroformylation-reduction hydrogenation cascade reaction. CN107866282A discloses the application of a class of nitrogen-containing phosphine ligands in olefin hydroformylation-hydrogenation reduction cascade reaction. The nitrogen phosphine ligand disclosed in the invention has bifunctional characteristics, has both a phosphine ligand group coordinated with transition metal rhodium or ruthenium, and a secondary amine or imine nitrogen-containing group acting with protonic acid, which can realize olefin hydroformylation-hydrogenation cascade reaction, but the nitrogen phosphine ligand synthesis route is complicated and the raw material price is relatively expensive. Nozaki et al. (J.Am.Chem.Soc.2013,135,17393-17400) discloses a composite catalyst system combining a Rh-bisphosphite complex system and a Ru-Shvo catalytic system, which can realize the direct conversion of long-chain olefins to produce alcohols with a high carbon number. The catalytic system has a high reaction efficiency, but both catalysts are precious metals and the corresponding ligand prices are also relatively expensive. In summary, the above research results mainly catalyze the olefin hydroformylation-hydrogenation cascade reaction using catalysts composed of Rh or Ru compounds and complex phosphine nitrogen ligands. The catalyst preparation process is cumbersome and expensive, especially the preparation and synthesis route of complex phosphine nitrogen ligands is cumbersome, the raw materials are expensive and the yield is low, and it is a homogeneous catalytic process, which is not conducive to large-scale industrial application.

[0004] In view of the shortcomings of the prior art, there is an urgent need for a catalytic system with a simple preparation method and low price, and a multiphase catalytic reaction process, which can realize the direct conversion of olefins and synthesis gas into higher alcohols through a one-step method. In view of the characteristics of the olefin hydroformylation tandem reaction as the coupling of two chemical reaction processes, the catalytic system required for catalyzing the olefin hydroformylation tandem reaction needs to have a hydroformylation-hydrogenation dual catalytic active center to efficiently realize the olefin hydroformylation-hydrogenation tandem reaction. The composite catalyst system disclosed in the present invention has a hydroformylation and hydrogenation dual active center. By effectively mixing the two active centers, it is realized that under the multiphase composite catalyst system, olefins and synthesis gas are directly prepared into higher alcohols in one step, thereby achieving the purpose of synthesizing high value-added fine chemicals in one pot. Summary of the invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a method for directly preparing higher alcohols from olefins and synthesis gas. The reaction uses olefins and synthesis gas as raw materials and directly prepares higher alcohols in one step under the action of a composite catalyst.

[0006] To this end, the present invention provides a method for directly preparing higher alcohols from olefins and synthesis gas in one step, characterized in that olefins and synthesis gas are used as raw materials and directly converted to generate higher alcohols under the catalytic action of a composite catalyst; the composite catalyst is composed of a Rh-based multiphase catalyst as a first component and a Ni-based catalyst as a second component; the mass ratio of the first component to the second component is 1:50-10:1 (preferably 1:40-8:1, more preferably 1:25-5:1); the first component Rh-based multiphase catalyst is composed of a metal component Rh and an organic ligand polymer, and the organic ligand polymer is a polymer having a large specific surface area and a multi-level pore structure generated by solvent thermal polymerization of an organic P ligand containing a vinyl group; the second component Ni-based multiphase catalyst is composed of a main active component Ni, a metal additive, a selectivity improver and a carrier, the metal additive is selected from one or more of metals Ca, Ba, Li, and K; the selectivity improver is selected from one or more of metals Cu, Fe, Zn, and La; the carrier is selected from one or more of alumina, activated carbon, silica, and diatomaceous earth.

[0007] In one embodiment, the reaction temperature is 293-523K, the reaction pressure is 0.1-10.0MPa, and the gas volume space velocity is 100-10000h -1 The molar ratio of raw olefin to synthesis gas is 0.01:1-10:1.

[0008] In one embodiment, olefins are C 2-30 Chain olefins or C 6-30 One or more aromatic olefins to generate C2-C 30Higher alcohols; the synthesis gas comes from the synthesis gas production process using one or more of natural gas, coal, oilfield gas, coalbed methane or hydrocarbons as raw materials, the main components of the synthesis gas are H2 and CO, the volume content of H2 and CO is 40%-100%, and the volume ratio of H2 / CO is 0.1-10.0.

[0009] In one embodiment, the organic ligand polymer in the first component Rh-based heterogeneous catalyst refers to a polymer generated by solvent thermal polymerization of one or more organic P ligands containing vinyl groups; the organic P ligands containing vinyl groups are selected from one or more of the following:

[0010]

[0011] The metal active component Rh in the first component Rh-based heterogeneous catalyst accounts for 0.005%-20.0% (preferably 0.1%-5%) of the catalyst mass.

[0012] In one embodiment, the metal active component Ni in the second component Ni-based multiphase catalyst accounts for 40%-70% of the catalyst mass; the metal promoter (one or more of Ca, Ba, Li, K) accounts for 2%-10% of the catalyst mass; the selectivity improver (one or more of Cu, Fe, Zn, La) accounts for 0.1%-5% of the catalyst mass, and the remaining mass is the carrier.

[0013] In one embodiment, the second component Ni-based catalyst needs to be activated before being mixed with the first component to form a composite catalyst; the second component Ni-based catalyst activation process is divided into two steps; the first step is carried out in a reducing atmosphere containing one or two of H2 and CO, and the second step is carried out in a passivating atmosphere containing one or two of O2 and CO2; the reducing atmosphere or the passivating atmosphere does not contain or may also contain an inert atmosphere gas, and the inert atmosphere gas is one or more of He, N2, and Ar, and the volume content of the inert atmosphere gas is 0-99%.

[0014] In one embodiment, the activation conditions of the second component Ni-based catalyst are: activation temperature 273-773K, activation pressure 0-20.0MPa, activation gas volume space velocity 100-20000h -1 , activation time is 1-100h.

[0015] In one embodiment, the two components of the composite catalyst can be mixed in one of the following three ways: (1) powder mixing method: weigh the first component Rh-based catalyst and the second component Ni-based catalyst respectively, grind and mix them in a mortar according to the required mass ratio, press them into tablets, sieve them, and mix them evenly in particles according to the required mass ratio to form a composite catalyst; (2) particle mixing method: weigh the first component Rh-based catalyst and the second component Ni-based catalyst respectively, press them into tablets, sieve them, and mix them evenly in particles according to the required mass ratio to form a composite catalyst; (3) layered filling method: the catalyst bed is filled with the required mass of the first component Rh-based catalyst and the second component Ni-based catalyst in the order of the movement direction of the reaction materials in the reactor to obtain a composite catalyst; the powder mixing method is preferred.

[0016] The beneficial effects of the present invention include but are not limited to the following: 1) the olefin hydroformylation-reduction hydrogenation cascade reaction can avoid the separation and purification steps of the intermediate product, effectively reducing the generation of by-products; 2) at the same time, the reaction process can be shortened, the reaction energy consumption can be effectively reduced, and thus efficient and economical synthetic alcohol products can be achieved. The method of the present invention can be used to directly produce higher alcohols from olefins and synthesis gas in a one-step process, and the method has high economic value and broad prospects for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The present invention is a reaction process flow chart for directly converting olefins and synthesis gas into higher alcohols. DETAILED DESCRIPTION

[0018] In order to better illustrate the method for directly converting olefins and synthesis gas into higher alcohols in one step provided by the present invention and the preparation process of the composite catalyst thereof, the preparation of some composite catalyst samples and the examples of their application in the reaction process are given below, but the present invention is not limited to the examples listed. Unless otherwise specified, the contents and percentages in this application are calculated by "mass".

[0019] Example 1

[0020] 1) Preparation of the first component of the composite catalyst

[0021] At room temperature, 1g of tri(4-vinylbenzene)phosphite ligand, 1g of tri(4-vinylbenzene)phosphine and 0.05g of azobisisobutyronitrile were dissolved in 20ml of tetrahydrofuran solvent, stirred for 1h, and the mixed solution was polymerized at 120°C for 24h. After polymerization, the solvent was removed under reduced pressure to obtain a porous organic polymer containing phosphine ligands. At room temperature, 50.13mg of Rh(acac)(CO)2 and 2g of the prepared polymer were weighed and added to 50ml of ethanol solvent. After stirring for 24 hours, the solvent was removed under reduced pressure to obtain the first component of the composite catalyst, the Rh-based heterogeneous catalyst.

[0022] 2) Preparation of the second component of the composite catalyst

[0023] At 75°C, 84.2g Ni(NO3)2·6H2O, 15.4g Ba(NO3)2, and 2.8g La(NO3)3·6H2O were dissolved in 500ml water to form solution a, and 65.8g K2CO3 was dissolved in 500ml water to form solution b. Under stirring conditions, solution a was slowly dripped into solution b at a rate of 4ml / min. After the addition of solution a was completed, 9.8g silica powder was added to the mixed solution, and the mixture was filtered after high-speed stirring for 1h. The filter cake was dried at 120°C for 24h to obtain the second component of the composite catalyst, the Ni-based heterogeneous catalyst.

[0024] Activation conditions of the second component of the composite catalyst: 1) Reduction process: reducing gas 50% H2-50% Ar, reducing temperature 698K, reducing time 8h, reducing pressure 0.1MPa, reducing gas space velocity 1000h -1 ; 2) Passivation process: passivation gas 2% O2-98% Ar, passivation temperature 323K, passivation time 24h, passivation pressure 0.1MPa, passivation gas space velocity 2000h -1 After passivation, a pre-reduced second component of the composite catalyst is obtained.

[0025] 3) Mixing of two components of composite catalyst

[0026] Weigh 1 g of the first component Rh-based catalyst and 7 g of the pre-reduced second component Ni-based catalyst, grind and mix them evenly in a mortar, press them into tablets, and sieve them through 20-40 mesh to obtain a composite catalyst A.

[0027] 4) Composite catalyst test to evaluate reaction process

[0028] 4g of composite catalyst A was loaded into the middle of the tubular reactor, and quartz sand was filled at both ends. The mixed raw gas (C2H4:CO:H2=1:1:5) was introduced, and the mixed raw gas was directly fed in the form of gas. At 403K, 1MPa, and the mixed raw gas space velocity was 5000h -1 The reaction was carried out under the following conditions, and the reaction product was collected at 5°C in a collection tank equipped with circulating cooling. The obtained liquid product was analyzed by HP-7890N gas chromatography, and the internal standard method was used to analyze and calculate with anhydrous ethanol as the internal standard. The reaction results are listed in Table 1.

[0029] Example 2

[0030] 1) Preparation of the first component of the composite catalyst

[0031] The preparation method is the same as that of Example 1.

[0032] 2) Preparation of the second component of the composite catalyst

[0033] The preparation method is the same as that of Example 1.

[0034] 3) Mixing of two components of composite catalyst

[0035] The first component and the pre-reduced second component catalyst were respectively pressed into tablets, sieved through 20-40 meshes, and the two components were evenly mixed in a mass ratio of 1:7 to obtain a composite catalyst B.

[0036] 4) Composite catalyst test to evaluate reaction process

[0037] The evaluation of composite catalyst B was the same as in Example 1.

[0038] Example 3

[0039] 1) Preparation of the first component of the composite catalyst

[0040] The preparation method is the same as that of Example 1.

[0041] 2) Preparation of the second component of the composite catalyst

[0042] The preparation method is the same as that of Example 1.

[0043] 3) Mixing of two components of composite catalyst

[0044] 0.5 g of the first component catalyst and 3.5 g of the pre-reduced second component catalyst were sequentially filled into the reactor in the order of the moving direction of the reaction materials to obtain a composite catalyst C.

[0045] 4) Composite catalyst test to evaluate reaction process

[0046] The evaluation of composite catalyst C was the same as in Example 1.

[0047] Example 4

[0048] 1) Preparation of the first component of the composite catalyst

[0049] The preparation method is the same as that of Example 1.

[0050] 2) Preparation of the second component of the composite catalyst

[0051] The preparation method is the same as that of Example 1.

[0052] 3) Mixing of two components of composite catalyst

[0053] The mixing method of the two components of the composite catalyst is the same as in Example 1

[0054] 4) Composite catalyst test to evaluate reaction process

[0055] The reaction temperature of 418K replaced the reaction temperature of 403K in Example 1, and other small-scale test evaluation reaction process parameters were the same as in Example 1. The reaction results are listed in Table 1.

[0056] Example 5

[0057] 1) Preparation of the first component of the composite catalyst

[0058] The preparation method is the same as that of Example 1.

[0059] 2) Preparation of the second component of the composite catalyst

[0060] The preparation method is the same as that of Example 1.

[0061] 3) Mixing of two components of composite catalyst

[0062] The mixing method of the two components of the composite catalyst is the same as in Example 1

[0063] 4) Composite catalyst test to evaluate reaction process

[0064] The reaction pressure of 5 MPa replaced the reaction pressure of 1 MPa in Example 1, and other small-scale test evaluation reaction process parameters were the same as in Example 1. The reaction results are listed in Table 1.

[0065] Example 6

[0066] 1) Preparation of the first component of the composite catalyst

[0067] The preparation method is the same as that of Example 1.

[0068] 2) Preparation of the second component of the composite catalyst

[0069] The preparation method is the same as that of Example 1.

[0070] 3) Mixing of two components of composite catalyst

[0071] The mixing method of the two components of the composite catalyst is the same as in Example 1

[0072] 4) Composite catalyst test to evaluate reaction process

[0073] The mixed raw gas (C3H6:CO:H2=1:1:5) replaced the mixed raw gas (C2H4:CO:H2=1:1:5) in Example 1, and the mixed raw gas was directly fed in the form of gas. Other small-scale test evaluation reaction process parameters were the same as those in Example 1. The reaction results are listed in Table 1.

[0074] Example 7

[0075] 1) Preparation of the first component of the composite catalyst

[0076] The preparation method is the same as that of Example 1.

[0077] 2) Preparation of the second component of the composite catalyst

[0078] The preparation method is the same as that of Example 1.

[0079] 3) Mixing of two components of composite catalyst

[0080] The mixing method of the two components of the composite catalyst is the same as in Example 1

[0081] 4) Composite catalyst test to evaluate reaction process

[0082] Liquid olefin 1-octene feedstock and synthesis gas (C8H 16 :CO:H2 molar ratio = 1:1:5) replaced the mixed raw material gas in Example 1 (C2H4:CO:H2 = 1:1:5), wherein the liquid olefin 1-octene raw material was fed into the reaction system in the form of a high-pressure pump, and the synthesis gas was directly fed in the form of gas. Other small-scale test evaluation reaction process parameters were the same as those in Example 1. The reaction results are listed in Table 1.

[0083] Comparative Example 1

[0084] 1) Preparation of the first component of the composite catalyst

[0085] The preparation method is the same as that of Example 1.

[0086] 2) Preparation of the second component of the composite catalyst

[0087] The catalyst preparation method is the same as that in Example 1 except that the catalyst activation process is not performed after the preparation of the second component of the composite catalyst is completed.

[0088] 3) Mixing of two components of composite catalyst

[0089] The mixing method of the other two components of the composite catalyst is the same as that of Example 1, except that the second component of the composite catalyst involved in the mixing method is a catalyst that has not been pre-reduced.

[0090] 4) Composite catalyst test to evaluate reaction process

[0091] Before the evaluation of the composite catalyst in a small test, the catalyst activation process was first carried out. The catalyst activation conditions were the same as those in Example 1, and the specific steps were as follows: 1) Reduction process: reducing gas 50% H2-50% Ar, reducing temperature 698K, reducing time 8h, reducing pressure 0.1MPa, reducing gas space velocity 1000h -1 ; 2) Passivation process: passivation gas 2% O2-98% Ar, passivation temperature 323K, passivation time 24h, passivation pressure 0.1MPa, passivation gas space velocity 2000h -1 .

[0092] The evaluation of other composite catalysts was carried out in the same manner as in Example 1. The reaction results are listed in Table 1.

[0093] Table 1. Results of the one-step process of preparing higher alcohols from olefins and synthesis gas

[0094]

[0095] Examples 1-7 and Comparative Example 1 give the reaction data of olefin and synthesis gas in one step to prepare higher alcohol. The difference between Examples 1-3 is that the mixing methods of the first component and the second component of the catalyst are different, and the other catalyst preparation methods and reaction evaluation conditions are consistent. In Example 1, when the two components are mixed in powder mode, the olefin conversion rate is 92.8% and the alcohol selectivity is 90.5%; in Example 2, when the two components are mixed in particles, the olefin conversion rate is 91.2% and the alcohol selectivity is 85.6%; in Example 3, when the two components are filled in layers, the olefin conversion rate is 80.5% and the alcohol selectivity is 76.8%. The reaction results of Examples 1-3 show that when the two components are mixed in powder mode, the composite catalyst has the best olefin conversion rate and higher alcohol selectivity in the one-step direct preparation of higher alcohol reaction of olefin and synthesis gas. The difference between Example 1 and Comparative Example 1 is that the activation process of the second component of the composite catalyst occurs at different times, and the other catalyst preparation methods and reaction evaluation conditions are consistent. In Example 1, the second component activation process occurred before the two components were mixed, and the olefin conversion rate was 92.8%, and the alcohol selectivity was 90.5%; in Comparative Example 1, the second component activation process occurred after the two components were mixed, and the olefin conversion rate was 15.6%, and the alcohol selectivity was 6.7%. The reaction results of Example 1 and Comparative Example 1 show that the second component activation process occurred before the two components were mixed, and the composite catalyst has significantly better reaction activity and higher alcohol selectivity.

[0096] From the above results, it can be seen that the method for directly preparing higher alcohols by one-step conversion of olefins and synthesis gas provided by the present invention has the following main advantages: 1) the olefin hydroformylation-reduction hydrogenation tandem reaction can avoid the separation and purification steps of intermediate products, effectively reducing the generation of by-products; 2) at the same time, the reaction process can be shortened, the reaction energy consumption can be effectively reduced, and thus efficient and economical synthetic alcohol products can be achieved. The method of the present invention can make olefins and synthesis gas directly prepare higher alcohols in a one-step process, and the method has high economic value and broad prospects for industrial application.

[0097] The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It is understood by those skilled in the art that other changes and modifications may be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A method for directly preparing higher alcohols from olefins and synthesis gas in one step, characterized in that: Using olefins and synthesis gas as raw materials, they are directly converted into higher alcohols under the catalytic action of a composite catalyst; The composite catalyst is formed by mixing a Rh-based heterogeneous catalyst as a first component and a Ni-based catalyst as a second component; the mass ratio of the first component to the second component is 1:50-10:1; The first component Rh-based heterogeneous catalyst is composed of a metal component Rh and an organic ligand polymer, wherein the organic ligand polymer is a polymer having a large specific surface area and a multi-level pore structure generated by solvent thermal polymerization of an organic P ligand containing a vinyl group; The second component Ni-based heterogeneous catalyst is composed of the main active component Ni, a metal promoter, a selectivity improver and a carrier, wherein the metal promoter is selected from one or more of metals Ca, Ba, Li and K; the selectivity improver is selected from one or more of metals Cu, Fe, Zn and La; and the carrier is selected from one or more of alumina, activated carbon, silicon dioxide and diatomaceous earth; The second component Ni-based catalyst needs to be activated before being mixed with the first component to form a composite catalyst; The activation process of the second component Ni-based catalyst is divided into two steps; the first step is carried out in a reducing atmosphere containing one or both of H2 and CO, and the second step is carried out in a passivating atmosphere containing one or both of O2 and CO2; The reducing atmosphere or the passivating atmosphere contains no or contains inert atmosphere gas, the inert atmosphere gas is one or more of He, N2, Ar, and the volume content of the inert atmosphere gas is 0-99%; The two components of the composite catalyst are mixed in one of the following two ways: (1) Powder mixing method: Weigh the first component Rh-based catalyst and the second component Ni-based catalyst respectively, grind and mix them evenly in a mortar according to the required mass ratio, press them into tablets, and sieve them to obtain a composite catalyst; (2) Particle mixing method: Weigh the first component Rh-based catalyst and the second component Ni-based catalyst separately, press them into tablets, sieve them, and mix them evenly according to the required mass ratio to form a composite catalyst.

2. The method according to claim 1, characterized in that The mass ratio of the first component to the second component of the composite catalyst is 1:40-8:

1.

3. The method according to claim 1, characterized in that The mass ratio of the first component to the second component of the composite catalyst is 1:25-5:

1.

4. The method according to claim 1, characterized in that Reaction temperature 293-523 K, reaction pressure 0.1-10.0 MPa, gas volume space velocity 100-10000 h -1 The molar ratio of raw olefin to synthesis gas is 0.01:1-10:

1.

5. The method according to claim 4, characterized in that Reaction temperature 323-423 K, reaction pressure 0.5-6.0 MPa, gas volume space velocity 500-8000 h -1 The molar ratio of raw olefins to synthesis gas is 0.05:1-5:

1.

6. The method according to claim 1, characterized in that The olefin is C 2-30 Chain olefins or C 6-30 One or more aromatic olefins to generate C2-C 30 Higher alcohols; the synthesis gas comes from the synthesis gas production process using one or more of natural gas, coal, oilfield gas, coalbed methane or hydrocarbons as raw materials, the main components of the synthesis gas are H2 and CO, the volume content of H2 and CO is 40%-100%, and the volume ratio of H2 / CO is 0.1-10.

0.

7. The method according to claim 6, characterized in that The volume content of H2 and CO in the synthesis gas is 80%-100%, and the volume ratio of H2 / CO is 0.5-8.

0.

8. The method according to claim 1, characterized in that The organic ligand polymer in the first component Rh-based heterogeneous catalyst refers to a polymer generated by solvent thermal polymerization of one or more organic P ligands containing vinyl groups; the organic P ligands containing vinyl groups are selected from one or more of the following: ， The metal active component Rh in the first component Rh-based heterogeneous catalyst accounts for 0.005%-20.0% of the catalyst mass.

9. The method according to claim 8, characterized in that The metal active component Rh in the first component Rh-based heterogeneous catalyst accounts for 0.1%-5% of the catalyst mass.

10. The method according to claim 1, characterized in that In the second component Ni-based heterogeneous catalyst, the metal active component Ni accounts for 40%-70% of the catalyst mass; the metal promoter accounts for 2%-10% of the catalyst mass; the selectivity improver accounts for 0.1%-5% of the catalyst mass, and the rest is the carrier.

11. The method according to claim 10, characterized in that In the second component Ni-based heterogeneous catalyst, the metal active component Ni accounts for 45%-65% of the catalyst mass; the metal promoter accounts for 4-7% of the catalyst mass; the selectivity improver accounts for 0.4-2% of the catalyst mass, and the rest is the carrier.

12. The method according to claim 1, characterized in that The activation conditions of the second component Ni-based catalyst are as follows: activation temperature 273-773 K, activation pressure 0-20.0 MPa, activation gas volume space velocity 100-20000 h -1 , activation time is 1-100 h.

13. The method according to claim 12, characterized in that The activation conditions of the second component Ni-based catalyst are as follows: activation temperature 523-723 K, activation pressure 0.1-5.0 MPa, activation gas volume space velocity 500-5000 h -1 , activation time is 4-60 h.

14. The method according to claim 1, characterized in that The two components of the composite catalyst are mixed in powder form.

Images