CN116143592A - Method for directly preparing higher alcohol by olefin and synthesis gas through one-step method - Google Patents

Method for directly preparing higher alcohol by olefin and synthesis gas through one-step method Download PDF

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CN116143592A
CN116143592A CN202111390273.8A CN202111390273A CN116143592A CN 116143592 A CN116143592 A CN 116143592A CN 202111390273 A CN202111390273 A CN 202111390273A CN 116143592 A CN116143592 A CN 116143592A
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catalyst
gas
olefin
composite catalyst
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姜淼
严丽
丁云杰
王国庆
李存耀
马雷
孙钊
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a method for directly preparing higher alcohol from olefin and synthetic gas by a one-step method. The composite catalyst is formed by taking an Rh-based multi-phase catalyst as a first component and mixing with an Ni-based multi-phase catalyst as a second component. The first component Rh-based multi-phase catalyst consists of a metal component Rh and an organic ligand polymer, wherein the organic ligand polymer is a porous polymer formed by solvothermal polymerization of organic P ligands containing vinyl. The second component Ni-based multi-phase catalyst consists of main active component Ni, metal auxiliary agent, selectivity improver and carrier. The reaction process of the method has higher raw material conversion rate and target product yield, and effectively reduces the energy consumption in the reaction process. The invention provides a new route for directly preparing higher alcohol from olefin and synthetic gas by a one-step method, and has wide application prospect.

Description

Method for directly preparing higher alcohol by olefin and synthesis gas through one-step method
Technical Field
The invention relates to a method for directly preparing higher alcohol by an olefin and synthesis gas one-step method, belonging to the technical field of heterogeneous catalysis.
Background
The hydroformylation of olefins is carried out with synthesis gas (CO and H) 2 Mixed gas) is reacted under the action of a transition metal complex catalyst to produce aldehydes or alcohols having one more carbon atom than the original olefin, and thus produced aldehydes, alcohols and derivatives thereof are used in large amounts as plasticizers, surfactants, solvents, fragrances and the like, and at present, about more than 2200 ten thousand tons of aldehydes and alcohols are produced worldwide each year using olefin hydroformylation technology. However, in most cases, the product aldehyde is often not the final product, and the aldehyde group activity is utilized to further convert it into more valuable fine chemicals, such as the olefin hydroformylation-reduction hydrogenation tandem reaction, which is the most commercially useful, capable of directly obtaining the target product alcohol in a "one-pot" reaction. The olefin hydroformylation-reduction hydrogenation tandem reaction can avoid the steps of separation and purification of intermediate products, and effectively reduce the generation of byproducts; meanwhile, the reaction process flow can be shortened, and the reaction energy consumption can be effectively reduced, so that the efficient and economical synthesis of alcohol products is realized.
At present, a plurality of researches on olefin hydroformylation-reduction hydrogenation tandem reactions are reported. CN107866282a discloses the use of a class of nitrogen-containing phosphine ligands in olefin hydroformylation-hydrodeoxygenation tandem reactions. The nitrogen-phosphine ligand disclosed by the invention has the dual-function characteristic, has phosphine ligand groups coordinated with transition metal rhodium or ruthenium and secondary amine or imine nitrogen-containing groups reacting with protonic acid, and can realize olefin hydroformylation-hydrogenation tandem reaction, but the synthesis route of the nitrogen-phosphine ligand is complex and the raw material price is high. Nozaki et al (J.am.chem.Soc.2013, 135, 17393-17400) disclose a composite catalyst system combining a Rh-bisospsphite complex system and a Ru-Shvo catalytic system, which can realize direct conversion of long-chain olefins to prepare alcohols with one carbon number higher. The catalytic system has higher reaction efficiency, but both catalysts are noble metals and the corresponding ligands are expensive. In summary, the above-mentioned research results mainly refer to the catalysis of olefin hydroformylation-hydrogenation tandem reactions with catalysts composed of Rh or Ru compounds and complex phosphine-nitrogen ligands. The catalyst has the advantages of complicated preparation process and high price, particularly the complicated preparation and synthesis route of the complex phosphine-nitrogen ligand, high raw material price and low yield, is a homogeneous catalysis process, and is unfavorable for large-scale industrial application.
Aiming at the defects of the prior art, a catalytic system with simple preparation method and low price is urgently needed, and the catalytic system is a heterogeneous catalytic reaction process, so that the direct conversion of olefin and synthesis gas into higher alcohol through a one-step method is realized. In view of the characteristic that the olefin hydroformylation tandem reaction is coupled with two chemical reaction processes, a catalytic system required for catalyzing the olefin hydroformylation tandem reaction needs to have a hydroformylation-hydrogenation double-catalytic active center so as to efficiently realize the olefin hydroformylation-hydrogenation tandem reaction. The composite catalyst system disclosed by the invention has a hydroformylation active center and a hydrogenation active center, and the two active centers are effectively mixed, so that the purpose of synthesizing high-added-value fine chemicals by a one-pot method is realized by directly preparing higher alcohols from olefin and synthesis gas through one step under the heterogeneous composite catalyst system.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for directly preparing higher alcohol from olefin and synthesis gas, wherein the reaction takes the olefin and the synthesis gas as raw materials, and the higher alcohol is directly prepared by a one-step method under the action of a composite catalyst.
Therefore, the invention provides a method for directly preparing higher alcohol by an olefin and synthesis gas one-step method, which is characterized in that the olefin and the synthesis gas are used as raw materials, and are directly converted into the higher alcohol under the catalysis of a composite catalyst; the composite catalyst is formed by mixing an Rh-based multi-phase catalyst serving as a first component and a Ni-based catalyst serving 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 multi-phase catalyst consists of a metal component Rh and an organic ligand polymer, wherein the organic ligand polymer is a polymer with a large specific surface area and a multistage pore structure generated by solvothermal polymerization of an organic P ligand containing vinyl; the second component Ni-based multi-phase catalyst consists of main active component Ni, metal auxiliary agent, selectivity improver and carrier, wherein the metal auxiliary agent is one or more than two of metals Ca, ba, li, K; the selectivity improver is one or more than two metals Cu, fe, zn, la; the carrier is one or more than two of alumina, activated carbon, silicon dioxide and diatomite.
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 the raw olefin to the synthesis gas is 0.01:1-10:1.
In one embodiment, the olefin is C 2-30 Chain olefins or C 6-30 One or more than two of aromatic olefins to generate C 2 -C 30 Higher alcohols; the synthesis gas is derived from a synthesis gas making process taking one or more than two of natural gas, coal, oilfield gas, coal bed gas or hydrocarbon as raw materials, and the main component of the synthesis gas is H 2 And CO, H 2 And the volume content of CO is 40-100%, H 2 The volume ratio of the catalyst to CO is 0.1-10.0.
In one embodiment, the organic ligand polymer in the first component Rh-based multi-phase catalyst refers to a polymer formed by solvothermal polymerization of one or more vinyl-containing organic P ligands; the organic P ligand containing vinyl is selected from one or more than two of the following:
Figure BDA0003364846770000031
the metal active component Rh in the first component Rh-based multi-phase catalyst accounts for 0.005% -20.0% (preferably 0.1% -5%) of the mass of the catalyst.
In one embodiment, the metal active component Ni in the second component Ni-based multi-phase catalyst accounts for 40-70% of the mass of the catalyst; one or more than two metal assistants (Ca, ba, li, K) account for 2-10% of the mass of the catalyst; the selectivity improver (one or more than two of Cu, fe, zn, la) accounts for 0.1-5% of the mass of the catalyst, and the rest is the carrier.
In one embodiment, the second component Ni-based catalyst requires an activation treatment prior to mixing with the first component to form a composite catalyst; the second component Ni-based catalyst activation procedure is divided into two steps; the first step is to contain H 2 One or two of CO under a reducing atmosphere, the second step being carried out in a atmosphere containing O 2 、CO 2 One or two of the following steps are performed under a passivation atmosphere; the reducing atmosphere or passivation atmosphere does not contain or can also contain inert atmosphere gas, and the inert atmosphere gas is He or N 2 One or more than two of Ar and 0-99% of inert atmosphere gas.
In one embodiment, the second component Ni-based catalyst activation conditions are: the activation temperature is 273-773K, the activation pressure is 0-20.0MPa, and the volume space velocity of the activated gas is 100-20000h -1 The activation time is 1-100h.
In one embodiment, the two components of the composite catalyst may be mixed in one of three ways: (1) powder mixing mode: respectively weighing a first component Rh-based catalyst and a second component Ni-based catalyst, grinding and uniformly mixing in a mortar according to a required mass ratio, tabletting, forming and sieving to obtain a composite catalyst; (2) particle mixing mode: respectively weighing a first component Rh-based catalyst and a second component Ni-based catalyst, respectively tabletting, forming, sieving, and uniformly mixing particles according to a required mass ratio to form a composite catalyst; (3) layered packing mode: the catalyst bed layer is sequentially filled with a first component Rh-based catalyst and a second component Ni-based catalyst with required mass according to the sequence of the reactor along the movement direction of the reaction materials to obtain a composite catalyst; the powder mixing mode is preferred.
The beneficial effects of the invention include, but are not limited to, the following: 1) The olefin hydroformylation-reduction hydrogenation tandem reaction can avoid the steps of separation and purification of intermediate products, and effectively reduce the generation of byproducts; 2) Meanwhile, the reaction process flow can be shortened, and the reaction energy consumption can be effectively reduced, so that the efficient and economical synthesis of alcohol products is realized. The method can directly prepare the higher alcohol from the olefin and the synthetic gas through a one-step method, and has higher economic value and wide industrial application prospect.
Drawings
FIG. 1 is a flow chart of a reaction process for the direct conversion of olefins and synthesis gas to higher alcohols.
Detailed Description
In order to better illustrate the method for directly converting higher alcohols by the one-step method of olefin and synthesis gas and the preparation process of the composite catalyst, the preparation of some composite catalyst samples and the application of the composite catalyst samples in the reaction process are shown below, but the invention is not limited to the examples. Unless otherwise specifically indicated, the amounts and percentages herein are by mass.
Example 1
1) Preparation of first component of composite catalyst
1g of tris (4-vinylbenzene) phosphonite ligand, 1g of tris (4-vinylbenzene) phosphine and 0.05g of azobisisobutyronitrile were dissolved in 20ml of tetrahydrofuran solvent at room temperature, stirred for 1 hour, and then the above mixed solution was polymerized at 120℃for 24 hours, and after polymerization, the solvent was removed under reduced pressure to obtain a porous organic polymer containing phosphine ligand. 50.13mg Rh (acac) (CO) was weighed out at room temperature 2 And 2g of the polymer prepared above was added to 50ml of ethanol solvent, stirred for 24 hours, and then the solvent was removed under reduced pressure to obtain a composite catalyst, rh-based multi-phase catalyst, as a first component.
2) Preparation of the second component of the composite catalyst
At 75℃84.2g Ni (NO 3 ) 2 ·6H 2 O、15.4g Ba(NO 3 ) 2 、2.8g La(NO 3 ) 3 ·6H 2 O was dissolved in 500ml of water to form solution a, 65.8. 65.8g K 2 CO 3 Dissolved in 500ml of water to form solution b. Solution a was slowly dropped into solution b at a rate of 4ml/min with stirring. After the completion of the dropwise addition of the solution a, 9.8g of silica powder was added to the mixed solution, followed by stirring at high speed for 1 hour, filtration, and cake 120Drying for 24 hours at the temperature of C to obtain the second component Ni-based multi-phase catalyst of the composite catalyst.
Activation conditions of the second component of the composite catalyst: 1) The reduction process comprises the following steps: reducing gas 50% H 2 50% Ar, reducing temperature 698K, reducing time 8h, reducing pressure 0.1MPa, reducing gas space velocity 1000h -1 The method comprises the steps of carrying out a first treatment on the surface of the 2) And (3) passivating: passivation gas 2%O 2 -98% Ar, passivation temperature 323K, passivation time 24h, passivation pressure 0.1MPa, passivation gas space velocity 2000h -1 . And (3) passivating to obtain the pre-reduced composite catalyst second component.
3) Two components of composite catalyst are mixed
1g of a first component Rh-based catalyst and 7g of a pre-reduced second component Ni-based catalyst are weighed, ground and uniformly mixed in a mortar, pressed into tablets and sieved by a 20-40-mesh sieve, and then the composite catalyst A is obtained.
4) Composite catalyst small scale evaluation reaction process
4g of composite catalyst A was charged into the middle of the tubular reactor, and both ends were filled with quartz sand. Introducing the mixed raw material gas (C) 2 H 4 :CO:H 2 =1:1:5), the mixed feed gas was directly fed in gaseous form. At 403K,1MPa, mixed feed gas space velocity 5000h -1 The reaction was carried out under the conditions that the reaction product was collected at 5℃by a collecting tank equipped with circulating cooling. The obtained liquid phase product is analyzed by HP-7890N gas chromatography, and is analyzed and calculated by an internal standard method by taking absolute ethyl alcohol as an internal standard. The reaction results are shown in Table 1.
Example 2
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
And respectively tabletting and forming the first component and the pre-reduced second component catalyst, sieving with a 20-40 mesh sieve, and uniformly mixing the two components according to the mass ratio of 1:7 to obtain the composite catalyst B.
4) Composite catalyst small scale evaluation reaction process
Composite catalyst B was evaluated as in example 1.
Example 3
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
The composite catalyst C was obtained by filling 0.5g of the first component catalyst and 3.5g of the pre-reduced second component catalyst in this order in the direction of movement of the reaction mass.
4) Composite catalyst small scale evaluation reaction process
Composite catalyst C was evaluated as in example 1.
Example 4
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
The method for mixing the two components of the composite catalyst is the same as in example 1
4) Composite catalyst small scale evaluation reaction process
Reaction temperature 418K was used in place of reaction temperature 403K in example 1, and other pilot-scale reaction process parameters were the same as in example 1. The reaction results are shown in Table 1.
Example 5
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
The method for mixing the two components of the composite catalyst is the same as in example 1
4) Composite catalyst small scale evaluation reaction process
The reaction pressure 5MPa was used in place of the reaction pressure 1MPa in example 1, and other pilot-scale evaluation reaction process parameters were the same as those in example 1. The reaction results are shown in Table 1.
Example 6
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
The method for mixing the two components of the composite catalyst is the same as in example 1
4) Composite catalyst small scale evaluation reaction process
Mixed feed gas (C) 3 H 6 :CO:H 2 =1:1:5) instead of the mixed raw material gas (C) in example 1 2 H 4 :CO:H 2 =1:1:5), the mixed feed gas was also fed directly in gaseous form, and the other pilot-scale reaction process parameters were the same as in example 1. The reaction results are shown in Table 1.
Example 7
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The preparation method is the same as in example 1.
3) Two components of composite catalyst are mixed
The method for mixing the two components of the composite catalyst is the same as in example 1
4) Composite catalyst small scale evaluation reaction process
Liquid olefin 1-octene feedstock and synthesis gas (C) 8 H 16 :CO:H 2 Molar ratio=1:1:5) instead of the mixed feed gas (C) in example 1 2 H 4 :CO:H 2 =1:1:5), wherein a liquid olefin 1-octene feedstock was fed to the reaction system in the form of a high pressure pump, synthesis gas was fed directly or in the form of a gas, and other pilot-scale reaction process parameters were as in example 1. Reaction results columnTable 1 shows the results.
Comparative example 1
1) Preparation of first component of composite catalyst
The preparation method is the same as in example 1.
2) Preparation of the second component of the composite catalyst
The procedure for the preparation of the catalyst was as in example 1, except that the catalyst activation process was not performed after the preparation of the second component of the composite catalyst.
3) Two components of composite catalyst are mixed
The two component mixing process for the remaining composite catalyst was the same as in example 1 except that the second component of the composite catalyst involved in the mixing process was a catalyst that was not pre-reduced.
4) Composite catalyst small scale evaluation reaction process
Before the test evaluation of the composite catalyst, the catalyst activation process is carried out, and the catalyst activation conditions are the same as in example 1, and the specific steps are as follows: 1) The reduction process comprises the following steps: reducing gas 50% H 2 50% Ar, reducing temperature 698K, reducing time 8h, reducing pressure 0.1MPa, reducing gas space velocity 1000h -1 The method comprises the steps of carrying out a first treatment on the surface of the 2) And (3) passivating: passivation gas 2%O 2 -98% Ar, passivation temperature 323K, passivation time 24h, passivation pressure 0.1MPa, passivation gas space velocity 2000h -1 。
Other composite catalyst pilot evaluations were as in example 1. The reaction results are shown in Table 1.
TABLE 1 one-step reaction of olefins and Synthesis gas to higher alcohols
Figure BDA0003364846770000081
Examples 1-7 and comparative example 1 give data on the one-step higher alcohols reaction of olefins with synthesis gas. Examples 1-3 differ in the manner in which the first and second components of the catalyst are mixed, and in that the other catalyst preparation methods and reaction evaluation conditions are consistent. Example 1, when the two components are mixed in powder mode, the conversion rate of olefin is 92.8%, and the selectivity of alcohol is 90.5%; example 2, when the two components are mixed in a particle mode, the conversion rate of olefin is 91.2%, and the selectivity of alcohol is 85.6%; example 3, two component split packing mode, olefin conversion 80.5% and alcohol selectivity 76.8%. The results of examples 1-3 show that the composite catalyst has optimal olefin conversion and higher alcohol selectivity in the reaction of directly preparing higher alcohol from olefin and synthesis gas in one step when the two components are mixed in powder mode. Example 1 differs from comparative example 1 in that the activation process of the second component of the composite catalyst occurs at different times, and other catalyst preparation methods and reaction evaluation conditions are identical. Example 1, the second component activation process occurs before mixing of the two components, with 92.8% olefin conversion and 90.5% alcohol selectivity; comparative example 1, the second component activation process occurred after mixing of the two components with 15.6% conversion of olefin and 6.7% alcohol selectivity. The results of the reactions of example 1 and comparative example 1 show that the second component activation process occurs before the two components are mixed and that the composite catalyst has significantly more excellent reactivity and higher alcohol selectivity.
From the above results, the method for directly preparing higher alcohols by one-step conversion of olefin and synthesis gas provided by the invention has the main advantages that: 1) The olefin hydroformylation-reduction hydrogenation tandem reaction can avoid the steps of separation and purification of intermediate products, and effectively reduce the generation of byproducts; 2) Meanwhile, the reaction process flow can be shortened, and the reaction energy consumption can be effectively reduced, so that the efficient and economical synthesis of alcohol products is realized. The method can directly prepare the higher alcohol from the olefin and the synthetic gas through a one-step method, and has higher economic value and wide industrial application prospect.
The invention has been described in detail above but is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (8)

1. A method for directly preparing higher alcohol by an olefin and synthesis gas one-step method is characterized in that the olefin and the synthesis gas are used as raw materials, and are directly converted into the higher alcohol under the catalysis of a composite catalyst;
the composite catalyst is formed by mixing an Rh-based multi-phase catalyst serving as a first component and a Ni-based catalyst serving 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 multi-phase catalyst consists of a metal component Rh and an organic ligand polymer, wherein the organic ligand polymer is a polymer with a large specific surface area and a multistage pore structure generated by solvothermal polymerization of an organic P ligand containing vinyl;
the second component Ni-based multi-phase catalyst consists of main active component Ni, metal auxiliary agent, selectivity improver and carrier, wherein the metal auxiliary agent is one or more than two of metals Ca, ba, li, K; the selectivity improver is one or more than two metals Cu, fe, zn, la; the carrier is one or more than two of alumina, activated carbon, silicon dioxide and diatomite.
2. The process according to claim 1, wherein the reaction temperature is 293-523K (preferably 323-423K), the reaction pressure is 0.1-10.0MPa (preferably 0.5-6.0 MPa), and the gas volume space velocity is 100-10000h -1 (preferably 500-8000h -1 ) The molar ratio of feed olefin to synthesis gas is from 0.01:1 to 10:1 (preferably from 0.05:1 to 5:1).
3. The process according to claim 1, wherein the olefin is C 2-30 Chain olefins or C 6-30 One or more than two of aromatic olefins to generate C 2 -C 30 Higher alcohols; the synthesis gas is derived from a synthesis gas making process taking one or more than two of natural gas, coal, oilfield gas, coal bed gas or hydrocarbon as raw materials, and the main component of the synthesis gas is H 2 And CO, H 2 And a CO content of 40% to 100% (preferably 80% to 100%) by volume, H 2 The volume ratio of CO is 0.1-10.0 (preferably 0.5-8.0).
4. The method according to claim 1, wherein the organic ligand polymer in the first component Rh-based multi-phase catalyst is one or more polymers formed by solvothermal polymerization of vinyl-containing organic P ligands; the organic P ligand containing vinyl is selected from one or more than two of the following:
Figure FDA0003364846760000011
the metal active component Rh in the first component Rh-based multi-phase catalyst accounts for 0.005% -20.0% (preferably 0.1% -5%) of the mass of the catalyst.
5. The method according to claim 1, wherein the metal active component Ni in the second component Ni-based multi-phase catalyst accounts for 40% -70% (preferably 45% -65%) of the catalyst mass; one or more than two metal auxiliary agents (Ca, ba, li, K) account for 2-10 percent (preferably 4-7 percent) of the mass of the catalyst; the selectivity improver (one or more than two of Cu, fe, zn, la) accounts for 0.1% -5% (preferably 0.4-2%) of the mass of the catalyst, and the rest is the carrier.
6. The method of claim 1, wherein the second component Ni-based catalyst requires an activation treatment prior to mixing with the first component to form a composite catalyst;
the second component Ni-based catalyst activation procedure is divided into two steps; the first step is to contain H 2 One or two of CO under a reducing atmosphere, the second step being carried out in a atmosphere containing O 2 、CO 2 One or two of the following steps are performed under a passivation atmosphere;
the reducing atmosphere or passivation atmosphere does not contain or can also contain inert atmosphere gas, and the inert atmosphere gas is He or N 2 One or more than two of Ar and 0-99% of inert atmosphere gas.
7. The method of claim 6, wherein the second component Ni-based catalyst activation conditions are: activation temperature 273-773K (preferably 523-723K) The activating pressure is 0-20.0MPa (preferably 0.1-5.0 MPa), and the volume space velocity of the activating gas is 100-20000h -1 (preferably 500-5000h -1 ) The activation time is 1-100h (preferably 4-60 h).
8. The method according to claim 1 or 6, wherein the two components of the composite catalyst are mixed in one of three ways:
(1) Powder mixing mode: respectively weighing a first component Rh-based catalyst and a second component Ni-based catalyst, grinding and uniformly mixing in a mortar according to a required mass ratio, tabletting, forming and sieving to obtain a composite catalyst;
(2) The particle mixing mode is as follows: respectively weighing a first component Rh-based catalyst and a second component Ni-based catalyst, respectively tabletting, forming, sieving, and uniformly mixing particles according to a required mass ratio to form a composite catalyst;
(3) The layered filling mode is as follows: the catalyst bed layer is sequentially filled with a first component Rh-based catalyst and a second component Ni-based catalyst with required mass according to the sequence of the reactor along the movement direction of the reaction materials to obtain a composite catalyst;
the powder mixing mode is preferred.
CN202111390273.8A 2021-11-19 2021-11-19 Method for directly preparing higher alcohol by olefin and synthesis gas through one-step method Pending CN116143592A (en)

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