CN112892601A - Method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde - Google Patents

Method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde Download PDF

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CN112892601A
CN112892601A CN201911218618.4A CN201911218618A CN112892601A CN 112892601 A CN112892601 A CN 112892601A CN 201911218618 A CN201911218618 A CN 201911218618A CN 112892601 A CN112892601 A CN 112892601A
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姜淼
丁云杰
严丽
王国庆
程显波
金明
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Dalian Institute of Chemical Physics of CAS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
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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
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • 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
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • 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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    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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Abstract

The invention relates to a method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde, which comprises the step of carrying out hydroformylation reaction on 3-cyclohexene-1-formaldehyde 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 generated by thermal polymerization of an organic P ligand containing vinyl through a solvent, 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, and has excellent reaction activity and selectivity and good reaction stability; the novel solid heterogeneous catalyst is adopted, so that the separation cost of the catalyst, reactants and products is reduced, and the method has a high industrial application prospect.

Description

Method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde
Technical Field
The invention relates to a method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde, belonging to the technical field of heterogeneous catalysis.
Background
The 3-cyclohexene-1-formaldehyde can be made into high-value chemical 1, 4-cyclohexane dicarbaldehyde through hydroformylation reaction, and the 1, 4-cyclohexane dimethanol can be made through hydrogenation reaction process. 1, 4-cyclohexanedicarboxaldehyde is a starting material for the initial synthesis of carbocyclic spiro compounds and has been noted by researchers, and can be widely used as thermotropic liquid crystal modules in the field of optical displays and screen manufacturing. 1, 4-cyclohexane dimethanol is a good monomer for producing high value-added polyester materials, and polyester fibers produced by partially or completely replacing ethylene glycol have lower density, higher melting point and other heat properties, and are more excellent in hydrolytic stability and insulating property compared with polyethylene terephthalate, so that the 1, 4-cyclohexane dimethanol is widely used for producing films, resins for electronic products, insulating wires and the like.
Hydroformylation, which is a reaction of an olefin with synthesis gas to form 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 generate aldehyde from raw olefin under less harsh conditions, 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 nanofiltration and the reaction result is not ideal.
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)2The 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.
Sudheesh et al (Journal of Molecular Catalysis A: Chemical, 2008, 296: 61-70) HRh (CO) (PPh)3)3The catalyst is encapsulated in the 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)3The in-situ catalytic system encapsulated in the HMS mesoporous molecular sieve is applied to the hydroformylation reaction of propylene, and the HMS mesoporous molecular sieve is used as a nano-scale reactor, shows higher stability in a recycling experiment and has the same stability as that of a propylene hydroformylation reactorThere is still a large gap in reactivity compared to homogeneous catalytic systems.
Ki-Chang Song et al (Catalysis Today,2011,164:561-4(CO)12Reacting with amino group modified on inner surface to obtain Rh4(CO)12Immobilized on SBA-15. Another method is to directly modify the surface of SBA-15 with N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane through Rh4(CO)12Reacting with amino modified on the inner and outer surfaces of the molecular sieve to Rh4(CO)12Immobilized 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 added4(CO)12More 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.
In summary, the above general idea of studying homogeneous heterogenization of hydroformylation is to make organic functional groups interact with a homogeneous catalyst, so that the homogeneous catalyst is immobilized on a heterogeneous carrier, the biggest problem of the methods is the loss of the homogeneous catalyst, and the problem of activity reduction of the homogeneous catalyst immobilized on the carrier, which hinder large-scale industrial application of the homogeneous heterogenization technology of hydroformylation, study a novel homogeneous heterogenization technology of hydroformylation, and solve the main problem facing to the present is the main direction of studying the homogeneous heterogenization catalytic system of hydroformylation.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for preparing 1, 4-cyclohexanedicarboxaldehyde from 3-cyclohexene-1-formaldehyde, wherein a novel solid heterogeneous catalyst is adopted to make 3-cyclohexene-1-formaldehyde undergo a heterogeneous hydroformylation reaction to prepare the high-value chemical 1, 4-cyclohexanedicarboxaldehyde, and the method has high economy and wide industrial application prospects.
To this end, the present invention provides a process for producing 1, 4-cyclohexanedicarboxaldehyde from 3-cyclohexene-1-carbaldehyde, which comprises subjecting 3-cyclohexene-1-carbaldehyde 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 backbone of the organic ligand polymer, and by which the 3-cyclohexene-1-carbaldehyde can be subjected to heterogeneous hydroformylation reaction to produce the high-value chemical 1, 4-cyclohexanedicarboxaldehyde.
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 ligand containing a vinyl group is selected from one or more of the following:
Figure BDA0002300183320000041
in a preferred embodiment, the reaction conditions of 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-1Liquid volume space velocity of 0.01-10.0h-1。
In a preferred embodiment, the synthesis gas source is a gas-making process using natural gas, coal, oil field gas, coal bed gas or hydrocarbons as raw material, and the main component of the synthesis gas is H2And CO, H2And CO in an amount of 20 to 100% by volume, H2The volume ratio of/CO is 0.5-5.0.
In a preferred embodiment, the molar ratio of the 3-cyclohexene-1-carbaldehyde feedstock 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 100-3000m2Per g, pore volume of 0.1-5.0cm3(ii)/g, the pore size distribution is 0.1-200.0 nm.
In a preferred embodiment, the inert gas is Ar, N2And one or more of He.
In a preferred embodiment, when the reactor is a fixed bed, the heterogeneous hydroformylation of the 3-cyclohexene-1-carbaldehyde feed is carried out continuously over the solid heterogeneous catalyst, the resulting liquid product is continuously discharged from the reactor and collected by a product collection tank at-100 ℃ 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 and good reaction stability. The method can be used for preparing the high-value chemical 1, 4-cyclohexane dicarbaldehyde by the multiphase hydroformylation reaction of the 3-cyclohexene-1-formaldehyde, and has higher economical efficiency and wide industrial application prospect.
Drawings
FIG. 13 is a flow chart of a reaction process for preparing 1, 4-cyclohexanedicarboxaldehyde from cyclohexene-1-carbaldehyde.
Detailed Description
In order to better illustrate the preparation method of the catalyst and the application thereof in the reaction of preparing 1, 4-cyclohexane-dicarbaldehyde in high-value chemicals through heterogeneous hydroformylation of 3-cyclohexene-1-formaldehyde, 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
Under the protection of 298K and inert gas Ar, 10.0 g of tris (4-vinylbenzene) phosphine is dissolved in 100ml of tetrahydrofuran solvent, 0.25 g of azobisisobutyronitrile as a radical initiator is added to the solution, and the mixture is 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 (with the specific surface area of 1800 m) containing the phosphine ligand2Per g, pore volume of 0.4cm3(ii)/g, pore size distribution is 0.1-200.0 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)2CO is 1:1) and raw material 3-cyclohexene-1-formaldehyde, 3-cyclohexene-1-formaldehyde is conveyed into a reaction system by a high-pressure pump, and synthesis gas is directly fed in a gas form. At the hourly space velocity of 413K, 5.0MPa and 3-cyclohexene-1-formaldehyde solution of 0.15h-1The space velocity of the synthesis gas is 500h-1The 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 obtained liquid phase product is analyzed by HP-7890N gas chromatography, an internal standard method is adopted, and N-propanol is used as an internal standard for analysis and calculation. The reaction results are shown in Table 1.
Example 2
In example 2, the procedure was the same as in example 1 except that 7.0 g of tris (4-vinylphenyl) ylphosphine ligand and 3.0 g of tris (3-vinylphenyl) ylphosphine ligand were weighed out in place of 10.0 g of tris (4-vinylphenyl) ylphosphine ligand 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 5.2258 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 the synthesis gas feedstock (H) is used2CO 2:1 as a substitute for syngas feedstock (H)2CO 1:1) was used for the evaluation of the heterogeneous hydroformylation reaction, 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 the synthesis gas feedstock (H) is used21:2 CO instead of syngas feedstock (H)2CO 1:1) was used for the evaluation of the heterogeneous hydroformylation reaction, 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. The procedure was as in example 1, except that reaction temperature 373K was used instead of 413K for the evaluation of the heterogeneous hydroformylation reaction. 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 393K was used instead of 413K 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 pressure of 1MPa was used instead of the reaction pressure of 5MPa 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. Except that the raw material 3-cyclohexene-1-formaldehyde liquid is adopted, the hourly space velocity is 0.5h-1Substitute liquid hourly space velocity0.15h-1The other procedure was the same as in example 1. 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 the raw material 3-cyclohexene-1-formaldehyde liquid is adopted, the hourly space velocity is 0.05h-1Substitute liquid hourly space velocity of 0.15h-1The other procedure was the same as in example 1. The reaction results are shown in Table 1.
TABLE 1.3 heterogeneous hydroformylation results of cyclohexene-1-carbaldehyde
Figure BDA0002300183320000071
Figure BDA0002300183320000072
Figure BDA0002300183320000081
From the results, the solid heterogeneous catalyst provided by the invention is used for the hydroformylation reaction of 3-cyclohexene-1-formaldehyde, and has excellent reaction activity and selectivity and good reaction stability; because the novel solid heterogeneous catalyst is adopted, the separation cost of the catalyst, reactants and products is reduced, and the method is suitable for large-scale industrial production. The method can be used for preparing the high-value chemical 1, 4-cyclohexane dicarbaldehyde by the multiphase hydroformylation reaction of the 3-cyclohexene-1-formaldehyde, and has higher economical efficiency and wide industrial application prospect.
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 (8)

1. A method for preparing 1, 4-cyclohexanedicarboxaldehyde from 3-cyclohexene-1-formaldehyde, which is characterized in that the method comprises the step of subjecting 3-cyclohexene-1-formaldehyde 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, and the method can be used for subjecting 3-cyclohexene-1-formaldehyde to heterogeneous hydroformylation reaction to prepare the 1, 4-cyclohexanedicarboxaldehyde.
2. The process according to claim 1, wherein the metal component is one or more of the metals Rh, Co, Ir or Ru, said metal component constituting from 0.005% to 20.0% (preferably from 0.01% to 5.0%) by weight of the total solid heterogeneous catalyst.
3. The method of claim 1, wherein the organic ligand polymer is a polymer produced by the thermal polymerization of a vinyl-containing organic P ligand in a solvent, wherein the vinyl-containing organic P ligand is selected from one or more of the following:
Figure FDA0002300183310000011
4. the process of claim 1, wherein the reaction conditions of the hydroformylation reaction are: the reaction temperature is 293-573K (preferably 323-523K), the reaction pressure is 0.1-20.0MPa (preferably 0.5-10.0MPa), and the gas volume space velocity is 100-20000h-1(preferably 500-10000 h)-1) Liquid volume space velocity of 0.01-10.0h-1(preferably 0.02-8.0 h)-1)。
5. 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 H2And CO, H2And CO in a volume content of 20% to 100% (preferably 50% to 10)0％)，H2The volume/CO ratio is between 0.5 and 5.0 (preferably between 0.8 and 4.0).
6. The process according to claim 1, wherein the molar ratio of the 3-cyclohexene-1-carbaldehyde feedstock to the synthesis gas is from 0.001:1 to 10:1 (preferably from 0.01:1 to 8: 1).
7. The method as claimed in claim 1, wherein the specific surface area of the organic ligand polymer is 100-3000m2Per g, pore volume of 0.1-5.0cm3(ii)/g, the pore size distribution is 0.1-200.0 nm.
8. The process as claimed in claim 1, wherein when the reactor is a fixed bed, the 3-cyclohexene-1-carbaldehyde heterogeneous hydroformylation reaction is continuously carried out over the solid heterogeneous catalyst, the resulting liquid product continuously flows out of the reactor and is collected at-100 ℃ through a product collection tank, and the resulting liquid product is further treated by rectification or flash distillation to obtain a high-purity product.
CN201911218618.4A 2019-12-03 2019-12-03 Method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde Pending CN112892601A (en)

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