CN118047666A - Olefin hydroformylation multiphase reaction method - Google Patents
Olefin hydroformylation multiphase reaction method Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000004821 distillation Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000012621 metal-organic framework Substances 0.000 claims description 5
- 239000010412 oxide-supported catalyst Substances 0.000 claims description 5
- -1 ethylene, propylene, butene Chemical class 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 17
- 239000010948 rhodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of supported heterogeneous catalysts, and discloses a multiphase reaction method for olefin hydroformylation. The olefin hydroformylation multiphase reaction method comprises the following steps: 1) A step of subjecting a C2-C7 olefin to an olefin hydroformylation reaction with a mixture of hydrogen and carbon monoxide in the presence of an olefin hydroformylation heterogeneous catalyst in the presence of an optional solvent; 2) Distilling the reaction product, wherein the distillation process enables the active components desorbed from the supported heterogeneous catalyst in the reaction process to be supported on the carrier again; 3) The distillation residue is used as olefin hydroformylation heterogeneous catalyst in step 1). The olefin hydroformylation multiphase reaction method can effectively avoid the loss of active components in the supported multiphase catalyst, and can realize secondary load between the free active metal center and the carrier in the separation process, thereby obviously improving the recyclability of the supported multiphase catalyst.
Description
Technical Field
The invention relates to the field of supported heterogeneous catalysts, in particular to a multiphase reaction method for olefin hydroformylation.
Background
At present, the hydroformylation reaction still uses a homogeneous catalyst mainly comprising rhodium-phosphine complex, and the catalyst has high activity and selectivity, but has high difficulty in subsequent separation treatment and high cost, especially in long-chain olefin reaction. Meanwhile, the phosphine-containing ligand has high price and is sensitive to water, and the like, so that the industrial development of the hydroformylation reaction is restricted.
Compared with a homogeneous catalyst, the heterogeneous catalyst has the advantages of simple preparation process, low cost, easy separation of the catalyst and reaction materials, and the like, but the heterogeneous catalyst has the problem of active component loss during filtration and separation, so that the catalytic performance cannot be maintained during recycling. Therefore, how to solve the problem of the cycle stability of the heterogeneous catalyst, so as to obtain the heterogeneous catalyst with simple preparation flow, low cost and good cycle stability is a research hot spot in the field at present.
CN107999061a discloses a heterogeneous catalyst prepared by loading nano metal rhodium on magnesium silicate nano tube and a preparation method thereof, the preparation flow of the method is simple, and the obtained heterogeneous catalyst has higher activity and selectivity when catalyzing olefin hydroformylation reaction to prepare aldehyde. However, the loss of the carried active components is serious, the circulation stability is poor, and the conventional recovery methods such as centrifugal separation, washing and drying can only be used for 3 times at most.
KausikMukhopadhyay et al (CHEM MATER,2003, 15:1766-1777) creatively immobilized HRh (CO) (PPh 3)3) on the inner surface of molecular sieves after treatment and post-modification of MCM-41 and MCM-48 molecular sieves, but the obtained catalyst has low reaction activity, serious metal loss during recycling and poor reusability.
The general ideas of the research on homogeneous phase heterogeneous are that active components are loaded on a carrier through adsorption, bonding and other methods, and then the catalyst is recovered through solid-liquid separation methods such as filtration, centrifugation and the like, and the biggest problem of the methods at present is the problem of loss of the active components in the recycling process of the heterogeneous catalyst, and the problem is the biggest bottleneck for restricting the application of the hydroformylation heterogeneous catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an olefin hydroformylation multiphase reaction method which can effectively avoid the loss of active components in a supported multiphase catalyst and realize secondary loading between a free active metal center and a carrier in a separation process, thereby remarkably improving the recyclability of the supported multiphase catalyst.
As described above, in the prior art, the catalyst was recovered by solid-liquid separation such as filtration and centrifugation, and the inventors of the present invention have found through intensive studies that the number of times of use of the supported heterogeneous catalyst can be remarkably increased by distilling out the reaction solvent and the product by distillation treatment in the olefin hydroformylation heterogeneous reaction to obtain distillation residues, since the active component desorbed from the supported heterogeneous catalyst during the reaction can be re-supported on the carrier during the distillation treatment, there is no loss of the active component, and thus the present invention has been completed.
The invention provides a multiphase reaction method for olefin hydroformylation, which is characterized by comprising the following steps of,
1) A step of subjecting a C2-C7 olefin to an olefin hydroformylation reaction with a mixture of hydrogen and carbon monoxide in the presence of an olefin hydroformylation heterogeneous catalyst in the presence of an optional solvent;
2) Distilling the reaction product obtained in the step 1) to obtain at least part of the solvent and/or at least part of the product and distillation residues, wherein the distillation treatment enables the active components desorbed from the supported heterogeneous catalyst in the reaction process to be supported on the carrier again;
3) The distillation residue is used as olefin hydroformylation heterogeneous catalyst in step 1).
Preferably, the olefin hydroformylation heterogeneous catalyst is one or more of a metal organic framework material supported catalyst, a carbon material supported catalyst, a metal oxide supported catalyst, a molecular sieve supported catalyst and a porous organic polymer supported catalyst.
Preferably, in case a solvent is used, in step 2) 82% by weight or more of said solvent, 82% by weight or more of said product is obtained; more preferably, 92% by weight or more of the solvent, 92% by weight or more of the product is obtained; more preferably, 97% by weight or more of the solvent, 97% by weight or more of the product is obtained; further preferably, 100% by weight of the solvent, 100% by weight of the product is obtained.
Preferably, in step 2) 82% by weight or more of the product is obtained without the use of solvents; more preferably, 92% by weight or more of the product is obtained; more preferably, 97% by weight or more of the product is obtained; further preferably, 100 wt% of the product is obtained.
Preferably, the active component is one or more of Rh, pd, ir, ru, co, fe, cu, zn, al, mg, ce, cs, li, na and K; more preferably, the active component is one or more of Rh, pd and Co.
Preferably, the conditions of the distillation treatment include: the temperature is 20-120 ℃ and the vacuum degree is 10-1000mbar.
Preferably, in step 1), the reaction conditions for hydroformylation of olefins include: the reaction temperature is 70-160 ℃, the pressure of the mixed gas is 0.5-10MPa, and the reaction time is 1-15 hours.
Preferably, in the mixed gas, the volume ratio of hydrogen to carbon monoxide is 1:0.4-2.5.
Preferably, the C2-C7 olefin is one or more of ethylene, propylene, butene, pentene, hexene and heptene.
Preferably, the C2-C7 olefin is butene and/or hexene.
Preferably, the distillation residue is recycled 10 times or more, preferably 1000 times or less.
Through the technical scheme, the olefin hydroformylation heterogeneous reaction method can effectively avoid loss of active components in the supported heterogeneous catalyst, and can realize secondary load between the free active metal center and the carrier in the separation process, thereby remarkably improving the recyclability of the supported heterogeneous catalyst.
And, the method of the present invention is general and applicable to catalysts including, but not limited to, metal organic framework Materials (MOFs) supported catalysts, carbon material supported catalysts, metal oxide supported catalysts, molecular sieve supported catalysts, porous organic polymer supported catalysts, and the like.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to the present invention there is provided a process for the heterogeneous reaction of hydroformylation of olefins, wherein the process comprises the steps of,
1) A step of subjecting a C2-C7 olefin to an olefin hydroformylation reaction with a mixture of hydrogen and carbon monoxide in the presence of an olefin hydroformylation heterogeneous catalyst in the presence of an optional solvent;
2) Distilling the reaction product obtained in the step 1) to obtain at least part of the solvent and/or at least part of the product and distillation residues, wherein the distillation treatment enables the active components desorbed from the supported heterogeneous catalyst in the reaction process to be supported on the carrier again;
3) The distillation residue is used as olefin hydroformylation heterogeneous catalyst in step 1).
According to the present invention, the olefin hydroformylation heterogeneous catalyst may be a heterogeneous catalyst generally used in the art for olefin hydroformylation. Preferably, the olefin hydroformylation heterogeneous catalyst is one or more of a metal organic framework material supported catalyst, a carbon material supported catalyst, a metal oxide supported catalyst, a molecular sieve supported catalyst and a porous organic polymer supported catalyst; more preferably, the olefin hydroformylation heterogeneous catalyst is one or more of a carbon material supported catalyst and a metal oxide supported catalyst.
In the present invention, "in the presence of an optional solvent" means that the reaction in step 1) may be carried out in the presence of a solvent or may not use a solvent. The specific solvent to be used or not may be appropriately selected by those skilled in the art depending on the starting olefin.
In the present invention, the active component of the olefin hydroformylation heterogeneous catalyst is not particularly limited, and various components generally carried on olefin hydroformylation heterogeneous catalyst carriers in the art can be exemplified by one or more of Rh, pd, ir, ru, co, fe, cu, zn, al, mg, ce, cs, li, na and K; preferably, the active component of the olefin hydroformylation heterogeneous catalyst is one or more of Rh, pd and Co; more preferably, the active components of the olefin hydroformylation heterogeneous catalyst are Rh and Co.
According to the present invention, the solvent may be various solvents commonly used in olefin hydroformylation heterogeneous catalytic reactions, for example, may be one or more of toluene, N-hexane and N, N-dimethylformamide, and is preferably toluene.
In the present invention, the amount of the solvent may be selected according to the amount of the C2-C7 olefin, and preferably, the volume ratio of the solvent to the C2-C7 olefin is 0.25-4:1, a step of; more preferably, the volume ratio of the solvent to the C2-C7 olefin is from 0.5 to 2:1.
In the present invention, preferably, the C2-C7 olefin is one or more of ethylene, propylene, butene, pentene, hexene and heptene; more preferably, the C2-C7 olefin is butene and/or hexene.
In the present invention, in the mixed gas of hydrogen and carbon monoxide, the volume ratio of hydrogen and carbon monoxide may be 1:0.4-2.5, preferably 1:0.5 to 1.8, for example, 1:1.
According to the present invention, it is preferable that the air in the reaction vessel is completely exhausted by introducing the mixed gas before introducing the mixed gas to perform the reaction. For example, the reaction vessel may be charged with the mixed gas to a pressure of 1.0MPa or more, and then the gas in the vessel may be discharged to a pressure of 0.1MPa or less, and the above-mentioned steps may be repeated 3 times or more.
In the present invention, preferably, the reaction conditions for hydroformylation of olefins include: the reaction temperature is 70-160 ℃, the pressure of the mixed gas is 0.5-10MPa, and the reaction time is 1-15 hours; more preferably, the reaction conditions for hydroformylation of olefins include: the reaction temperature is 90-120 ℃, the pressure of the mixed gas is 2-5MPa, and the reaction time is 2-6 hours.
According to the invention, in the case of using a solvent, the solvent is also included in the resulting reaction product comprising the supported heterogeneous catalyst and the product. At this point, in the distillation treatment of step 2), at least part of the solvent and/or at least part of the product and distillation residues are obtained.
In addition, the reaction product comprising the supported heterogeneous catalyst and the product is obtained without the use of solvents. At this time, at least part of the product is obtained in the distillation treatment of step 2).
Specifically, in the case of using a solvent, it is preferable that 82% by weight or more of the solvent and 82% by weight or more of the product are obtained in step 2); more preferably, 92% by weight or more of the solvent, 92% by weight or more of the product is obtained; more preferably, 97% by weight or more of the solvent, 97% by weight or more of the product is obtained; further preferably, 100% by weight of the solvent, 100% by weight of the product is obtained.
Furthermore, in the absence of a solvent, preferably in step 2) 82% by weight or more of the product is obtained; more preferably, 92% by weight or more of the product is obtained; more preferably, 97% by weight or more of the product is obtained; further preferably, 100 wt% of the product is obtained.
In the present invention, even if the solvent and/or the product remain in the distillation residue, since the distillation residue is used as the supported heterogeneous catalyst in step 1), no loss of the solvent and the product is caused.
According to the present invention, a part of the unreacted C2 to C7 olefins may be left in the reaction product, and at least a part of the remaining olefins may be separated by the distillation treatment when the C2 to C7 olefins are in a liquid state, or the remaining olefins may be separated as much as possible.
According to the invention, in step 2), the distillation treatment is carried out under conditions such that the solvent and the product are separated to give the distillation residue and the active ingredient is carried again. Preferably, the conditions of the distillation treatment include: the temperature is 20-120 ℃ and the vacuum degree is 10-1000mbar; more preferably, the conditions of the distillation treatment include: the temperature is 20-60 ℃ and the vacuum degree is 20-100mbar.
In the present invention, the reaction solvent and the product are distilled off by distillation treatment to obtain a distillation residue, and since the active component desorbed from the supported heterogeneous catalyst during the reaction is carried on the carrier again during the distillation treatment, there is no loss of the active component, and thus the number of times of recycling of the distillation residue can be significantly increased, for example, the number of times of recycling can be 10 times or more, preferably 20 times or more, further preferably 30 times or more; further, it is preferably 1000 times or less, more preferably 500 times or less, more preferably 100 times or less, more preferably 50 times or less, and further preferably 40 times or less.
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, are all commercially available.
In the examples below, room temperature is 25.+ -. 3 ℃.
Example 1
1) 20Mg of RhCl 3 was dissolved in 200ml of water, 1g of MIL101 (Cr) (purchased from Shanghai CHEMSOON) was weighed into the above solution, stirred at room temperature for 6 hours, then filtered, and the solid was dried under vacuum at 60℃to give a heterogeneous catalyst Rh@MIL101 (Cr).
2) 200Mg of heterogeneous catalyst Rh@MIL101 (Cr) was dispersed in 200mL of toluene in a 500mL autoclave, the autoclave was closed after sufficient displacement with inert gas, the autoclave was frozen to a low temperature with dry ice, and 20mL of the mixed olefins, each 50% by weight of butene-1 and butene-2 collected by freezing, was transferred to the frozen autoclave. Then adding H 2 in the volume ratio: co=1: 1 to the pressure of 3.0MPa, stirring and heating are started, timing is started after the temperature is raised to 100 ℃, and after 2 hours of reaction, the heating is closed to naturally cool the mixture to the room temperature. Releasing unreacted gas, taking a small amount of reaction mixture, placing the mixture into a centrifuge tube, centrifuging, taking supernatant, and quantitatively analyzing the reaction mixture by using an LC-MS (liquid chromatography-mass spectrometry) qualitative and Agilent 7890B gas chromatograph. The specific chromatographic conditions were as follows: the temperature of the sample injector was 300℃and the temperature of the detector was 300℃and AGILENT HP-5 capillary chromatography columns (30 m. Times.0.32 mm. Times.0.25 m). The temperature programming strip is as follows: the initial temperature was 35℃and after 6min, the temperature was increased to 250℃at 10℃per min.
3) All the mixed reaction liquid is transferred into a round bottom flask, all liquid components in the reaction liquid are distilled to a recovery bottle by using a Heidolph LABOROTA 4000 effective rotary evaporator, and the heterogeneous catalyst Rh@MIL101 (Cr) is left in the round bottom flask, so that the recovery and separation of the catalyst are realized. The spin steaming conditions are as follows: the vacuum degree is 100mbar, the rotating speed is 60r/min, and the rotary steaming temperature is gradually increased from room temperature to 50 ℃.
4) Adding 200mL of toluene into the heterogeneous catalyst recovered in the step 3), transferring to a high-pressure reaction kettle, fully replacing the high-pressure reaction kettle with inert gas, closing the reaction kettle, freezing the reaction kettle to a low temperature by using dry ice, and simultaneously transferring 10mL of mixed olefin of 50 weight percent of butene-1 and butene-2 collected by freezing to the frozen reaction kettle. Repeating the steps 2) -3), and carrying out the cycle stability test.
5) The above steps 2) to 4) were repeated, and 10 cycles of the stability test were performed, and the test results are shown in Table 1.
TABLE 1
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 1 | 72.5 | 92.3 | 63.4 |
| Example 1 (first cycle) | 72.7 | 91.8 | 62.9 |
| Example 1 (second cycle) | 73.0 | 92.6 | 63.2 |
| Example 1 (third cycle) | 72.8 | 91.8 | 62.8 |
| Example 1 (fourth cycle) | 72.6 | 91.8 | 62.9 |
| Example 1 (fifth cycle) | 72.5 | 91.7 | 63.1 |
| Example 1 (sixth cycle) | 72.7 | 92.0 | 63.2 |
| Example 1 (seventh cycle) | 72.5 | 92.0 | 62.9 |
| Example 1 (eighth cycle) | 72.6 | 91.9 | 63.1 |
| Example 1 (ninth cycle) | 72.8 | 92.1 | 63.0 |
| Example 1 (tenth cycle) | 72.9 | 92.0 | 62.9 |
In addition, the operations of the steps 2) to 4) are continuously repeated, 100 times of cycle stability tests are carried out, the conversion rate is over 72 percent, the aldehyde selectivity is over 91 percent, and the normal aldehyde selectivity is over 62 percent in 100 times of cycles.
Example 2
The procedure of example 1 was followed except that the heterogeneous catalyst support was changed to activated carbon (available from Allatin under the trade designation C112223) and the test results are shown in Table 2.
TABLE 2
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 2 | 76.2 | 91.4 | 52.0 |
| Example 2 (first cycle) | 75.9 | 91.5 | 51.8 |
| Example 2 (second cycle) | 76.3 | 91.7 | 52.2 |
| Example 2 (third cycle) | 76.2 | 91.6 | 51.7 |
| Example 2 (fourth cycle) | 76.3 | 91.2 | 51.8 |
| Example 2 (fifth cycle) | 76.1 | 91.3 | 52.4 |
| Example 2 (sixth cycle) | 75.9 | 91.5 | 51.9 |
| Example 2 (seventh cycle) | 76.3 | 91.4 | 52.3 |
| Example 2 (eighth cycle) | 76.3 | 91.5 | 51.9 |
| Example 2 (ninth cycle) | 75.9 | 91.4 | 51.6 |
| Example 2 (tenth cycle) | 76.2 | 91.7 | 51.7 |
Example 3
The procedure of example 1 was followed except that the heterogeneous catalyst support was changed to Al 2O3 powder (available from Allatin, cat. A102091) and the test results are shown in Table 3.
TABLE 3 Table 3
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 3 | 65.3 | 92.9 | 55.4 |
| Example 3 (first cycle) | 65.6 | 92.8 | 55.2 |
| Example 3 (second cycle) | 65.5 | 92.6 | 55.9 |
| Example 3 (third cycle) | 65.6 | 92.3 | 55.4 |
| Example 3 (fourth cycle) | 65.8 | 92.5 | 55.5 |
| Example 3 (fifth cycle) | 65.2 | 92.3 | 55.2 |
| Example 3 (sixth cycle) | 65.5 | 92.4 | 55.3 |
| Example 3 (seventh cycle) | 65.7 | 92.3 | 55.4 |
| Example 3 (eighth cycle) | 65.4 | 92.6 | 55.4 |
| Example 3 (ninth cycle) | 65.7 | 92.3 | 55.6 |
| Example 3 (tenth cycle) | 65.6 | 92.5 | 55.7 |
Example 4
The procedure of example 1 was followed except that the heterogeneous catalyst support was changed to SBA-15 (available from Allatin, M96613) and the test results are shown in Table 4.
TABLE 4 Table 4
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 4 | 75.9 | 90.9 | 65.7 |
| Example 4 (first cycle) | 75.6 | 90.8 | 65.2 |
| Example 4 (second cycle) | 75.8 | 90.6 | 65.9 |
| Example 4 (third cycle) | 75.4 | 90.7 | 65.3 |
| Example 4 (fourth cycle) | 75.8 | 90.4 | 65.5 |
| Example 4 (fifth cycle) | 75.2 | 90.6 | 65.1 |
| Example 4 (sixth cycle) | 75.3 | 90.4 | 65.8 |
| Example 4 (seventh cycle) | 75.6 | 90.4 | 65.7 |
| Example 4 (eighth cycle) | 75.3 | 90.3 | 65.7 |
| Example 4 (ninth cycle) | 75.5 | 90.6 | 65.6 |
| Example 4 (tenth cycle) | 75.4 | 90.6 | 65.8 |
Example 5
1) 20Mg of RhCl 3 was dissolved in 200ml of water, 1g of MIL101 (Cr) (purchased from Shanghai CHEMSOON) was weighed into the above solution, stirred at room temperature for 6 hours, then filtered, and the solid was dried under vacuum at 60℃to give a heterogeneous catalyst Rh@MIL101 (Cr).
2) 200Mg of heterogeneous catalyst Rh@MIL101 (Cr) was dispersed in 200mL of toluene in a 500mL autoclave, 100mL of 1-hexene was added and mixed uniformly, and the dispersion was transferred to a mechanically stirred autoclave having a volume of 500 mL. Firstly, a certain amount of air is introduced into the reactor with the volume ratio of 1:1 and CO, and the air in the kettle is replaced by the mixed gas of H 2 and CO, and the air is inflated and deflated three times. After the replacement, the mixture of H 2 and CO with the total pressure of 3MPa and the volume ratio of 1:1 is filled. Stirring and heating are started, timing is started after the temperature is raised to 100 ℃, and after the reaction is carried out for 3 hours, the heating is closed to naturally cool the mixture to the room temperature. And (3) placing a small amount of the reaction mixed solution into a centrifuge tube, centrifuging, taking supernatant, and quantitatively analyzing the reaction solution by using an LC-MS (liquid chromatography-mass spectrometry) qualitative and Agilent 7890B gas chromatograph. The specific chromatographic conditions were as follows: the temperature of the sample injector was 300℃and the temperature of the detector was 300℃and AGILENT HP-5 capillary chromatography columns (30 m. Times.0.32 mm. Times.0.25 m). The temperature programming strip is as follows: the initial temperature was 35℃and after 6min, the temperature was increased to 250℃at 10℃per min.
3) All the mixed reaction liquid is transferred into a round bottom flask, all liquid components in the reaction liquid are distilled to a recovery bottle by using a Heidolph LABOROTA 4000 effective rotary evaporator, and the heterogeneous catalyst Rh@MIL101 (Cr) is left in the round bottom flask, so that the recovery and separation of the catalyst are realized. The spin steaming conditions are as follows: the vacuum degree is 20mbar, the rotating speed is 60r/min, and the rotary evaporation temperature is gradually increased from room temperature to 60 ℃.
4) 200ML of toluene and 100mL of reactant (1-hexene) are added into the heterogeneous catalyst recovered in the step 3) and uniformly mixed, and the operations of the steps 2) -3) are repeated for carrying out the cycle stability test.
5) The above steps 2) to 4) were repeated, and 10 cycles of the stability test were performed, and the test results are shown in Table 5.
TABLE 5
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 5 | 85.3 | 96.4 | 75.1 |
| Example 5 (first cycle) | 85.4 | 96.5 | 75.3 |
| Example 5 (second cycle) | 85.3 | 96.3 | 75.2 |
| Example 5 (third cycle) | 85.6 | 96.6 | 75.1 |
| Example 5 (fourth cycle) | 85.3 | 96.2 | 75.4 |
| Example 5 (fifth cycle) | 85.5 | 96.3 | 75.2 |
| Example 5 (sixth cycle) | 85.3 | 96.6 | 75.3 |
| Example 5 (seventh cycle) | 85.2 | 96.7 | 75.3 |
| Example 5 (eighth cycle) | 85.4 | 96.6 | 75.5 |
| Example 5 (ninth cycle) | 85.6 | 96.5 | 75.2 |
| Example 5 (tenth cycle) | 85.6 | 96.8 | 75.3 |
Example 6
The procedure of example 5 was followed except that the heterogeneous catalyst support was changed to activated carbon (available from Allatin under the trade designation C112223) and the test results are shown in Table 6.
TABLE 6
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Example 6 | 82.5 | 96.2 | 53.3 |
| Example 6 (first cycle) | 82.8 | 95.9 | 52.6 |
| Example 6 (second cycle) | 82.7 | 96.0 | 52.4 |
| Example 6 (third cycle) | 826 | 96.3 | 52.1 |
| Example 6 (fourth cycle) | 82.6 | 96.4 | 52.1 |
| Example 6 (fifth cycle) | 82.4 | 96.3 | 52.3 |
| Example 6 (sixth cycle) | 82.3 | 96.1 | 53.1 |
| Example 6 (seventh cycle) | 82.5 | 96.3 | 53.4 |
| Example 6 (eighth cycle) | 82.4 | 96.2 | 52.8 |
| Example 6 (ninth cycle) | 82.1 | 96.2 | 52.6 |
| Example 6 (tenth cycle) | 82.3 | 96.4 | 52.4 |
Comparative example 1
The procedure of example 5 was followed except that the catalyst separation method in step 3) was changed to high-speed centrifugation to effect solid-liquid separation, the number of the cyclic reactions in step 4) was changed to 5, and the test results are shown in Table 7.
TABLE 7
| Conversion% | Aldehyde Selectivity% | Normal aldehyde selectivity% | |
| Comparative example 1 | 85.4 | 96.2 | 75.1 |
| Comparative example 1 (first cycle) | 78.3 | 96.3 | 75.2 |
| Comparative example 1 (second cycle) | 63.1 | 96.1 | 74.9 |
| Comparative example 1 (third cycle) | 50.3 | 96.5 | 75.1 |
| Comparative example 1 (fourth cycle) | 38.6 | 96.2 | 75.2 |
| Comparative example 1 (fifth cycle) | 21.5 | 96.6 | 75.3 |
As shown by the results in tables 1-7, the olefin hydroformylation heterogeneous reaction method provided by the invention can effectively avoid the loss of active components in the supported heterogeneous catalyst, and can realize secondary loading between the free active metal center and the carrier in the separation process, thereby obviously improving the recyclability of the supported heterogeneous catalyst. In contrast, in comparative example 1, in which the catalyst was recovered by centrifugation, the conversion rate was reduced to 21.5% in the fifth cycle, and the catalyst could not be reused.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A multiphase reaction method for hydroformylation of olefins, which is characterized by comprising the following steps,
1) A step of subjecting a C2-C7 olefin to an olefin hydroformylation reaction with a mixture of hydrogen and carbon monoxide in the presence of an olefin hydroformylation heterogeneous catalyst in the presence of an optional solvent;
2) Distilling the reaction product obtained in the step 1) to obtain at least part of the solvent and/or at least part of the product and distillation residues, wherein the distillation treatment enables the active components desorbed from the supported heterogeneous catalyst in the reaction process to be supported on the carrier again;
3) The distillation residue is used as olefin hydroformylation heterogeneous catalyst in step 1).
2. The process of claim 1, wherein the olefin hydroformylation heterogeneous catalyst is one or more of a metal organic framework material supported catalyst, a carbon material supported catalyst, a metal oxide supported catalyst, a molecular sieve supported catalyst, and a porous organic polymer supported catalyst.
3. The process according to claim 1, wherein in step 2) a solvent is used, 82% by weight or more of the solvent, 82% by weight or more of the product is obtained;
Preferably, 92% by weight or more of the solvent, 92% by weight or more of the product is obtained;
Preferably, 97% by weight or more of the solvent, 97% by weight or more of the product is obtained;
preferably, 100% by weight of the solvent, 100% by weight of the product is obtained.
4. The process according to claim 1, wherein in step 2) 82% by weight or more of the product is obtained without the use of solvents;
Preferably, 92% by weight or more of the product is obtained;
preferably, 97% by weight or more of the product is obtained;
Preferably, 100% by weight of the product is obtained.
5. The method of any one of claims 1-4, wherein the active component is one or more of Rh, pd, ir, ru, co, fe, cu, zn, al, mg, ce, cs, li, na and K;
preferably, the active component is one or more of Rh, pd and Co.
6. The method according to any one of claims 1 to 4, wherein the conditions of the distillation treatment include: the temperature is 20-120 ℃ and the vacuum degree is 10-1000mbar.
7. The process of any of claims 1-4, wherein in step 1), the reaction conditions for hydroformylation of olefins comprise: the reaction temperature is 70-160 ℃, the pressure of the mixed gas is 0.5-10MPa, and the reaction time is 1-15 hours.
8. The method according to any one of claims 1-4, wherein the volume ratio of hydrogen to carbon monoxide in the mixture is 1:0.4-2.5.
9. The process of any of claims 1-4, wherein the C2-C7 olefin is one or more of ethylene, propylene, butene, pentene, hexene and heptene.
10. The process of claim 9, wherein the C2-C7 olefin is butene and/or hexene.
11. A process according to any one of claims 1 to 3, wherein the distillation residue is recycled more than 10 times, preferably less than 1000 times.
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