CN112898138B - High-value utilization method of Fischer-Tropsch product - Google Patents

High-value utilization method of Fischer-Tropsch product Download PDF

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CN112898138B
CN112898138B CN201911218740.1A CN201911218740A CN112898138B CN 112898138 B CN112898138 B CN 112898138B CN 201911218740 A CN201911218740 A CN 201911218740A CN 112898138 B CN112898138 B CN 112898138B
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CN112898138A (en
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丁云杰
严丽
姜淼
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Dalian Institute of Chemical Physics of CAS
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    • 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
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    • 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
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
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    • B01J35/617—
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    • B01J35/633—
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

The invention relates to a method for high-value utilization of a Fischer-Tropsch product, which comprises the step of carrying out hydroformylation reaction on the Fischer-Tropsch product and synthesis gas in a reactor in the presence of a solid heterogeneous catalyst, wherein the solid heterogeneous catalyst consists of one or more metal components Rh, Co, Ir or Ru and an organic ligand polymer, the organic ligand polymer is a polymer with a large specific surface area and a multistage pore structure, which is generated by carrying out solvent thermal polymerization on an organic P ligand containing vinyl, and the metal component and a P atom in the organic ligand polymer skeleton form a coordination bond. The method has simple and easy reaction process, is suitable for large-scale industrial production, has excellent reaction activity and selectivity, high normal-to-iso ratio of the product aldehyde and good reaction stability, and effectively improves the economy of indirect coal liquefaction.

Description

High-value utilization method of Fischer-Tropsch product
Technical Field
The invention relates to a high-value utilization method of a Fischer-Tropsch product, and belongs to the technical field of heterogeneous catalysis.
Background
At present, the main product of coal liquefaction is high-quality diesel mainly comprising straight-chain hydrocarbon, the economic benefit is not ideal, and the gasoline and diesel fraction section in the product of high-temperature iron-based slurry bed coal indirect liquefaction (medium-temperature Fischer-Tropsch) in China is rich in a large amount of olefin (about 65%), so how to convert the olefin into aldehyde, alcohol, ketone, ester and the like with high added values is one of the technical selectivity for improving the economy of the indirect liquefaction technology.
Through hydroformylation, the Fischer-Tropsch product containing more olefin is converted into oxygen-containing high-value chemicals, and the economy of indirect coal liquefaction can be effectively improved. Hydroformylation, which is a reaction of an olefin with synthesis gas to produce aldehydes having one more carbon than the starting olefin, is one of the most important industrial homogeneous catalytic reactions. Hydroformylation is a typical atom-economical reaction, and catalytic processes and catalysts thereof have been studied for nearly 60 years. Currently, approximately over 1200 million tons of aldehydes and alcohols are produced worldwide each year using olefin hydroformylation technology. The reaction can make the raw material olefin into aldehyde under the less harsh condition, and the product aldehyde can be further hydrogenated and converted into alcohol. The homogeneous catalysis system has higher catalytic activity and selectivity of target products under mild reaction conditions, but the separation problem of the catalyst and reaction materials is difficult, thus hindering large-scale industrial application of the homogeneous catalysis system. Compared with homogeneous catalysis, heterogeneous catalysis has the greatest advantages that the catalyst and reaction materials are easy to separate, and the main problems of the heterogeneous catalysis are harsh reaction conditions, relatively low reaction activity and the like. At present, the main research focus on hydroformylation is on developing a novel heterogeneous catalyst, which not only has the advantage of easy separation of heterogeneous catalytic catalyst and reaction materials, but also has high reaction activity and mild reaction conditions of homogeneous catalysis.
CN102281948A reports a polymer supported transition metal catalyst complex and method of use, producing a soluble polymer supported Rh catalyst with a narrower molecular weight distribution. However, the catalyst preparation, catalytic reaction and catalyst separation processes are complicated. The preparation of the catalyst requires that a functional monomer, styrene and the like are controlled to synthesize a soluble polymer, then a ligand is introduced, and finally the Rh catalyst is loaded. Compressed gas is required to be added in the catalytic reaction process. The catalyst is separated from the reaction mixture by adopting a nanofiltration mode, and the reaction result is not ideal.
U.S. p.5585524 reports a cobalt-based complex catalyst system for the hydroformylation of olefins to produce aldehydes which employs a two-phase organic polar/organic phase system such that the cobalt-based complex is separated from the organic phase by dissolution in the organic polarity. The catalyst system is applied to a cobalt carbonyl catalyst of ethylene. And the cobalt-based complex catalyst is simple to separate from the organic solvent and the product.
U.S. p.6184413 is a patent applied by university of california, reporting a supported phase catalyst whose supported phase is highly polar, such as ethylene glycol or glycerol; the metal center of the catalyst is chiral sulfonated 2, 2-bis (diphenylphosphino) -1, 1-bis (naphthyl) metal complex, the complex can be dissolved in a load phase, and the catalyst system can be used for asymmetric synthesis with optical activity.
Balue et al (J.mol.Catal.A., Chem,1999,137:193-203) use cation exchange resin as a carrier to form a heterogeneous catalyst by immobilizing rhodium sulfur compounds, and the cycle experiment of styrene hydroformylation shows that the heterogeneous catalyst has poor stability and the phenomenon of Rh loss is serious. Zeelie et al (appl.Catal.A: Gen, 2005,285:96-109) modified styrene and p-styrene diphenylphosphine on polyethylene fibers, Rh (acac) (CO) 2 The catalyst is anchored on a modified polyethylene fiber, and the ethylene hydroformylation result shows that the catalyst has higher conversion rate but poor stability under the conditions of 100 ℃ and 5bar, the reaction activity is sharply reduced after 50 hours of reaction, and the catalyst deactivation phenomenon is serious.
Ricken et al (J.mol.Catal.A: Chem,2006,257:78-88) subject the ligand NIXANTPHOS to various functional modifications, the modified ligand and Rh (acac) (CO) 2 The catalyst is loaded on a polyglycerol polymer, and the experiment of hydroformylation of 1-octene shows that the conversion rate of the catalyst can reach about 90% under the conditions of 80 ℃ and 20 bar. However, commercial purchase of polymeric carriers or prepared by conventional free radical styrene polymerization severely limits the industrial application of such catalysts due to problems of gel formation, polymer swelling, limited loading of phosphorus ligands in the polymer backbone, and loss of catalytically active components.
HRh (CO) (PPh) was prepared by passivating the exterior surface of MCM-41 and MCM-48 molecular sieves with diphenyldichlorosilane and then modifying the interior surface of the molecular sieves with 3-aminopropyltrimethoxysilane (Kausik Mukhopadhyay et al (Chem Mater,2003,15:1766- 3 ) 3 Selectively immobilized on the inner surface of the molecular sieve. The biggest highlight of this study is the creative reduction of HRh (CO) (PPh) 3 ) 3 The catalyst is selectively immobilized on the inner surfaces of MCM-41 and MCM-48 molecular sieves, but the reaction activity of the heterogeneous catalytic system is low in the view of the reaction effect of the catalyst, and a recycling experiment shows that the catalyst is poor in reusability and serious in metal loss.
Sudheesh et al (Journal of Molecular Catalysis A: Chemical, 2008, 296): 61-70) reacting HRh (CO) (PPh) 3 ) 3 The catalyst is encapsulated in an HMS mesoporous molecular sieve in situ and is applied to hydroformylation of long-chain olefin. The authors focus on the reaction of 1-hexene in a slurry bed, and discuss the effects of temperature, carbon monoxide partial pressure, hydrogen partial pressure, catalyst amount and the like on the reaction activity, and the catalyst recycling experiment shows that the catalyst has good reusability. Subsequently, N.Sudheesh et al (Applied Catalysis A: General,2012,415- 3 ) 3 The catalytic system in situ encapsulated in the HMS mesoporous molecular sieve is applied to hydroformylation of propylene, and the HMS mesoporous molecular sieve is used as a nanoscale reactor, shows higher stability in a recycling experiment, but has larger difference in reaction activity compared with a homogeneous catalytic system.
Ki-Chang Song et al (Catalysis Today,2011,164:561- 4 (CO) 12 Reacting with amino group modified on inner surface to obtain Rh 4 (CO) 12 Immobilized on SBA-15. Another method is to directly modify the surface of SBA-15 with N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane through Rh 4 (CO) 12 Reacting with amino modified on the inner and outer surfaces of the molecular sieve to Rh 4 (CO) 12 Immobilized on SBA-15. Researches show that the immobilized catalyst formed by the second treatment method has better activity and stability in hydroformylation reaction, and authors explain that the reason for better catalyst activity is that the internal and external surfaces are simultaneously modified to enable Rh to be added 4 (CO) 12 More evenly distributed on the inner and outer surfaces of the molecular sieve, thereby leading the homogeneous catalyst to have larger free space. The authors have shown that the higher n/i values of heterogeneous catalysts are due to steric hindrance of the ligands, favoring the formation of linear aldehydes.
US4252678 discloses the preparation of a colloidal dispersion containing a transition metal such as Rh, wherein the transition metal component is present in the form of a 1.0 to 20.0 nm colloidal dispersion in combination with a catalyst system comprising a hydroxy terminated (styrene/butadiene) functionalized copolymer and applied to the hydroformylation of 1-octene. The catalyst prepared by the method cannot be applied to fixed bed and trickle bed reactors, and the catalyst and the product are difficult to separate.
CN102281948A reports a polymer supported transition metal catalyst complex and method of use, producing a soluble polymer supported Rh catalyst with a narrower molecular weight distribution. However, the catalyst preparation, catalytic reaction and catalyst separation processes are complicated. The preparation of the catalyst requires that a functional monomer, styrene and the like are controlled to synthesize a soluble polymer, then a ligand is introduced, and finally the Rh catalyst is loaded. Compressed gas is required to be added in the catalytic reaction process. The catalyst is separated from the reaction mixture by nanofiltration and the reaction result is not ideal.
In summary, the general idea of the above-mentioned studies on homogeneous heterogenization is to make organic functional groups interact with a homogeneous catalyst, so as to make the homogeneous catalyst immobilized on a heterogeneous carrier, and the biggest problems of these methods are the loss of the homogeneous catalyst and the reduction of the activity of the homogeneous catalyst immobilized on the carrier, which are the biggest bottlenecks restricting the homogeneous immobilization of hydroformylation.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for high-value utilization of fischer-tropsch products, in which a novel solid heterogeneous catalyst is used to make fischer-tropsch products containing more olefins undergo a heterogeneous hydroformylation reaction to prepare oxygen-containing high-value chemicals, thereby effectively improving the economy of indirect coal liquefaction.
The invention provides a method for high-value utilization of Fischer-Tropsch products, which is characterized by comprising the step of subjecting the Fischer-Tropsch products and synthesis gas to hydroformylation reaction in a reactor in the presence of a solid heterogeneous catalyst, wherein the solid heterogeneous catalyst consists of a metal component and an organic ligand polymer, and the metal component forms a coordinate bond with a P atom in the organic ligand polymer skeleton.
In a preferred embodiment, the metal component is one or more of the metals Rh, Co, Ir or Ru.
In a preferred embodiment, the organic ligand polymer is a polymer having a large specific surface area and a hierarchical pore structure, which is produced by solvent thermal polymerization of an organic P ligand containing a vinyl group, wherein the organic P or N ligand containing a vinyl group is selected from one or more of the following:
Figure BDA0002300213790000051
in a preferred embodiment, the reaction conditions for the hydroformylation reaction are: the reaction temperature is 293-573K, the reaction pressure is 0.1-20.0MPa, and the gas volume space velocity is 100-20000h -1 Liquid volume space velocity of 0.01-10.0h -1 。
In a preferred embodiment, the Fischer-Tropsch product feed is C 2 -C 30 And oxygen-containing compounds of (A), and C 2 -C 30 The hydrocarbons of (a) contain olefins, and the olefins constitute from 5% to 90% of the total weight of the Fischer-Tropsch product feed.
In a preferred embodiment, the synthesis gas source is a gas-making process that is fed by natural gas, coal, oil field gas, coal bed gas or hydrocarbons, and the synthesis gas has a major component of H 2 And CO, H 2 And CO in an amount of 20 to 100% by volume, H 2 The volume ratio of/CO is 0.5-5.0.
In a preferred embodiment, the molar ratio of the Fischer-Tropsch product feed to the synthesis gas is from 0.001:1 to 10: 1.
In a preferred embodiment, the metal component comprises from 0.005% to 20.0% by weight of the total solid heterogeneous catalyst.
In a preferred embodiment, the specific surface area of the organic ligand polymer is 100-3000m 2 Per g, pore volume of 0.1-5.0cm 3 The pore size distribution is 0.1-200.0 nm.
In a preferred embodiment, the inert gas is Ar, N 2 And one or more of He.
In a preferred embodiment, when the reactor is a fixed bed, the Fischer-Tropsch product heterogeneous hydroformylation reaction is carried out continuously over the solid heterogeneous catalyst, the resulting liquid product continuously flows out of the reactor and is collected at-100 ℃ by a product collection tank, and the resulting liquid product is further processed by rectification or flash distillation to obtain a high purity product.
The benefits of the present invention include, but are not limited to, the following: compared with the existing hydroformylation reaction technology applied in industry, the novel solid heterogeneous catalyst is adopted, so that the separation cost of the catalyst, reactants and products is reduced; the reaction process is simple and easy to implement, is suitable for large-scale industrial production, and has excellent reaction activity and selectivity, high normal-to-iso ratio of the product aldehyde and good reaction stability. By using the method, the Fischer-Tropsch product containing more olefin can be prepared into oxygen-containing high-value chemicals through hydroformylation, and the economy of indirect coal liquefaction is effectively improved.
Drawings
FIG. 1 is a flow diagram of a reaction process for the continuous production of an oxygen-containing high value chemical from a Fischer-Tropsch product via a heterogeneous hydroformylation reaction in accordance with the present invention.
Detailed Description
In order to better illustrate the preparation method of the catalyst and the application thereof in the Fischer-Tropsch product heterogeneous hydroformylation reaction, the following examples of the preparation of some catalyst samples and the application thereof in the reaction process are given, but the invention is not limited to the examples. Unless otherwise specifically stated, the contents and percentages in the present application are calculated as "mass".
Example 1
6.5 g of tris (4-vinylphenyl) phosphine, 3.0 g of tris (3-vinylphenyl) phosphine and 0.5 g of biphephos phosphine ligand containing a vinyl group were dissolved in 100ml of tetrahydrofuran under an inert gas Ar protective atmosphere at 298KTo the above solution, 0.25 g of azobisisobutyronitrile, a radical initiator, was added and stirred for 0.5 hour. And transferring the stirred solution into a hydrothermal autoclave, and carrying out solvothermal polymerization for 24h under the protection of 373K and inert gas Ar. Cooling to room temperature after the polymerization, and removing the solvent in vacuum at 333K to obtain the porous organic polymer (the specific surface area of which is 1254 m) containing the phosphine ligand 2 G, pore volume of 1.95cm 3 (ii)/g, pore size distribution is 0.2-80.0 nm). 0.0627 g of rhodium acetylacetonate dicarbonyl are weighed out and dissolved in 100ml of tetrahydrofuran solvent under the protection of 298K and inert gas Ar, 10.0 g of the porous organic polymer containing phosphine ligand prepared above is added, and stirring is carried out for 24 hours. Subsequently, the solvent was evacuated under 333K temperature to obtain a solid heterogeneous catalyst in which the metal component was supported by the organic ligand polymer.
The solid heterogeneous catalyst prepared above was loaded into a fixed bed reactor, and quartz sand was loaded into both ends. Introduction of synthesis gas (H) 2 CO 1:1 and Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygen-containing compounds, the olefin content in the hydrocarbons is about 65 percent, and the oxygen-containing compounds are mainly C 3 -C 9 Monohydric alcohol) and naphtha feedstock are fed into the reaction system using a high pressure pump, with the synthesis gas being fed directly as a gas. At 373K, 1.0MPa and naphtha liquid hourly space velocity of 1.8h -1 Space velocity of synthesis gas 1250h -1 The hydroformylation reaction is carried out under the conditions. The reaction product was collected at 2.5 ℃ via a collection tank equipped with a recirculating cooler. The liquid phase product obtained was analyzed by HP-7890N gas chromatography and calculated by normalization. The reaction results are shown in Table 1.
Example 2
In example 2, the procedure was the same as in example 1 except that 10.0 g of tris (4-vinylphenyl) ylphosphine was weighed out instead of 6.5 g of tris (4-vinylphenyl) ylphosphine, 3.0 g of tris (3-vinylphenyl) ylphosphine and 0.5 g of biphephephosphine ligand having a vinyl group were dissolved in 100ml of tetrahydrofuran solvent. The reaction results are shown in Table 1.
Example 3
In example 3, the procedure was the same as in example 1 except that 3.4812 g of cobalt acetylacetonate was weighed out in place of 0.0627 g of rhodium acetylacetonate dicarbonyl in 100ml of tetrahydrofuran solvent. The reaction results are shown in Table 1.
Example 4
In example 4, the catalyst preparation procedure was the same as in example 1. Except that Fischer-Tropsch product feed (C) is used 4 -C 20 Hydrocarbons and oxygen-containing compounds, the olefin content being about 50%, the oxygen-containing compounds being mainly C 3 -C 9 Monohydric alcohol of) instead of Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygen-containing compounds, the olefin content in the hydrocarbons is about 65 percent, and the oxygen-containing compounds are mainly C 3 -C 9 Monohydric alcohol of (1) was used for the heterogeneous hydroformylation reaction evaluation, and the other procedures were the same as in example 1. The reaction results are shown in Table 1.
Example 5
In example 5, the catalyst preparation procedure was the same as in example 1. Except that Fischer-Tropsch product feed (C) is used 4 -C 18 Hydrocarbons and oxygen-containing compounds, the olefin content being about 20%, the oxygen-containing compounds being mainly C 3 -C 9 Monohydric alcohol of) instead of Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygen-containing compounds, the olefin content being about 65%, the oxygen-containing compounds being mainly C 3 -C 9 Monohydric alcohol) was used for heterogeneous hydroformylation evaluation, and the other procedures were the same as in example 1. The reaction results are shown in Table 1.
Example 6
In example 6, the catalyst preparation procedure was the same as in example 1. Using Fischer-Tropsch product feedstock (C) 2 -C 4 Hydrocarbons with an olefin content of about 60%) instead of the Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygen-containing compounds, the olefin content being about 65%, the oxygen-containing compounds being mainly C 3 -C 9 Monohydric alcohol of (a) was used for the heterogeneous hydroformylation reaction evaluation, and both the fischer-tropsch product feedstock and the synthesis gas were fed directly as gases. At 373K, 1.0MPa and Fischer-Tropsch product gas space velocity of 1000h -1 Space velocity of synthetic gas of 2000h -1 The hydroformylation reaction is carried out under the conditions. The liquid reaction phase product was collected at 2.5 ℃ via a collection tank equipped with a recycle cooler. The obtained liquid and gas phase produceThe material was analyzed by HP-7890N gas chromatography and calculated by normalization. The reaction results are shown in Table 1.
Example 7
In example 7, the catalyst preparation procedure was the same as in example 1. The procedure was the same as in example 1, except that 333K was used instead of 373K for the evaluation of the heterogeneous hydroformylation reaction. The reaction results are shown in Table 1.
Example 8
In example 8, the catalyst preparation procedure was the same as in example 1. The procedure was the same as in example 1, except that the reaction temperature 403K was used instead of the reaction temperature 373K for the evaluation of the heterogeneous hydroformylation reaction. The reaction results are shown in Table 1.
Example 9
In example 9, the catalyst preparation procedure was the same as in example 1. The procedure was the same as in example 1 except that the reaction pressure of 3MPa was used instead of the reaction pressure of 1MPa for evaluation of the heterogeneous hydroformylation reaction. The reaction results are shown in Table 1.
Example 10
In example 10, the catalyst preparation procedure was the same as in example 1. Except that Fischer-Tropsch product naphtha liquid hourly space velocity of 0.5h is adopted -1 Substitute liquid hourly space velocity of 1.8h -1 The other procedure was the same as in example 1. The reaction results are shown in Table 1.
Example 11
In example 11, the catalyst preparation procedure was the same as in example 1. Except that Fischer-Tropsch product naphtha liquid hourly space velocity is adopted for 4.0h -1 Substitute liquid hourly space velocity of 1.8h -1 The other procedure was the same as in example 1. The reaction results are shown in Table 1.
Comparative example 1
In comparative example 1, the catalyst preparation process was the same as in example 1. Except that the olefinic feedstock 1-octene is used instead of the Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygenates, olefin content about 65%) were evaluated for heterogeneous hydroformylation, and the other procedures were the same as in example 1. The reaction results are shown in Table 1.
Comparative example 2
In comparative example 2, the catalyst preparation process was the same as in example 1. Except that the olefinic feedstock 1-dodecene is used instead of the Fischer-Tropsch product naphtha feedstock (C) 4 -C 12 Hydrocarbons and oxygenates, olefin content about 65%) were evaluated for heterogeneous hydroformylation, and the other procedures were the same as in example 1. The reaction results are shown in Table 1.
Comparative example 3
In comparative example 3, except that SiO was used 2 The support was used in place of the porous organic polymer containing phosphine ligand for catalyst preparation and its subsequent evaluation of heterogeneous hydroformylation reaction, and the other procedure was the same as in example 1. The reaction results are shown in Table 1.
TABLE 1 Fischer-Tropsch product heterogeneous hydroformylation reaction results
Figure BDA0002300213790000091
Figure BDA0002300213790000101
As can be seen from the results of the reaction data of the above examples 1 to 11 and comparative examples 1 to 3, the solid heterogeneous catalyst provided by the invention is used for the hydroformylation of Fischer-Tropsch products, and the heterogeneous hydroformylation reaction process method designed and developed for specific Fischer-Tropsch products has excellent reactivity and selectivity, high normal-to-iso ratio of product aldehydes and good reaction stability; because of adopting the novel solid heterogeneous catalyst, the separation cost of the catalyst, the reactant and the product is reduced, and the method is suitable for large-scale industrial production. By using the catalyst provided by the invention, the Fischer-Tropsch product containing more olefin can be subjected to hydroformylation reaction to prepare oxygen-containing high-value chemical products, and the economy of indirect coal liquefaction is effectively improved.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art 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 (6)

1. A method for high-value utilization of Fischer-Tropsch products is characterized by comprising the steps of subjecting the Fischer-Tropsch products and synthesis gas to hydroformylation reaction in a reactor in the presence of a solid heterogeneous catalyst, wherein the solid heterogeneous catalyst consists of a metal component and an organic ligand polymer, and the metal component forms a coordinate bond with a P atom in a skeleton of the organic ligand polymer;
the Fischer-Tropsch product is Fischer-Tropsch synthesized naphtha, and the raw material of the Fischer-Tropsch synthesized naphtha is C 4 -C 12 Hydrocarbons and oxygen-containing compounds, the olefin content in the hydrocarbons being 65%, the oxygen-containing compounds being mainly C 3 -C 9 A monohydric alcohol of (a);
the metal component is metal Rh; the metal component accounts for 0.01 to 10.0 percent of the total weight of the solid heterogeneous catalyst;
the organic ligand polymer is prepared from tri (4-vinyl benzene) phosphine L1, tri (3-vinyl benzene) phosphine L7 and biphephos phosphine ligand L14 containing vinyl according to the mass ratio of 6.5: 3.0: 0.5 through solvent thermal polymerization;
Figure FDA0003704850190000011
the reaction conditions of the hydroformylation reaction are as follows: reaction temperature 373-573K, reaction pressure 1.0-20.0MPa, gas volume space velocity 1250h -1 Liquid volume space velocity of 0.01-1.8h -1 。
2. The method of claim 1, wherein the synthesis gas is derived from a gas-making process using natural gas, coal, oil field gas, coal bed gas, or hydrocarbons as a feedstock, and the synthesis gas has a major component of H 2 And CO, H 2 And CO in an amount of 20 to 100% by volume, H 2 The volume ratio of/CO is 0.5-5.0.
3. The process of claim 1 or 2, wherein the molar ratio of the fischer-tropsch product feedstock to the synthesis gas is in the range of from 0.001:1 to 10: 1.
4. The method as claimed in claim 1, wherein the specific surface area of the organic ligand polymer is 100-3000m 2 Per g, pore volume of 0.1-5.0cm 3 (ii)/g, the pore size distribution is 0.1-200.0 nm.
5. The process as claimed in claim 1, wherein when the reactor is a fixed bed, the Fischer-Tropsch product heterogeneous hydroformylation reaction is carried out continuously over the solid heterogeneous catalyst, the liquid product produced continuously flows out of the reactor and is collected at-100 ℃ by a product collection tank, and the resulting liquid product is further processed by distillation or flash distillation to obtain a high purity product.
6. The process of claim 3, wherein the molar ratio of the Fischer-Tropsch product feed to the synthesis gas is from 0.005:1 to 8: 1; h in synthesis gas 2 And CO in an amount of 50-100% by volume, H 2 The volume ratio of/CO is 0.8-4.0.
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