Method for improving recycling activity of asymmetric hydrogenation reaction catalyst

Abstract

The invention provides a method for improving the application activity of an asymmetric hydrogenation reaction catalyst. In the method, various index parameters of a stream for applying the catalyst should meet the following relational expression: # imgabs0 #, a is the content of an oxygen-containing solvent in the stream for applying, b is the total content of the catalyst in the stream for applying, c is the storage temperature of the stream for applying, and d is the storage time of the stream for applying. According to the method, the activity of the applied catalyst can be remarkably improved, and the stability of an operation device is greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of asymmetric hydrogenation reaction, and particularly relates to a method for improving the application activity of asymmetric hydrogenation reaction catalyst. Background Art

[0002] Asymmetric hydrogenation is one of the most efficient methods for preparing chiral compounds. It has perfect atom economy and has been widely used in industry after decades of development.

[0003] Asymmetric hydrogenation catalysts are mainly formed by the complexation of metal active centers with ligands. For example, HALPERN et al. conducted a detailed study on the complexation catalysts formed by rhodium metal and various chiral ligands (such as DIOP, BPPM, DIPHOS, etc.) in catalyzing the hydrogenation of dehydrogenated amino acids, and proposed the mechanism of rhodium-bisphosphine complex catalytic hydrogenation reaction. KLEMAN et al. used phosphine-phosphite ligands to modify rhodium precursors to form a series of catalysts, and used them in the hydrogenation reaction of enol esters, obtaining good reaction results.

[0004] Although the complex catalyst with metal active center and ligand has excellent catalytic performance, it also has obvious disadvantages. That is, during multiple applications, as the number of applications increases, the catalytic activity gradually decreases, and long-term stable application cannot be achieved, which in turn causes an increase in production costs. Summary of the invention

[0005] One of the purposes of the present invention is to provide a method for improving the catalytic activity of asymmetric hydrogenation reaction catalyst stream. The method can significantly improve the activity of the catalyst, and this discovery can greatly improve the stability of the operating device.

[0006] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solution:

[0007] A method for improving the activity of asymmetric hydrogenation reaction catalysts, wherein:

[0008] The parameters of the catalyst application stream should satisfy the following relationship:

[0009]

[0010] in:

[0011] a is the oxygen-containing solvent content in the applied stream, satisfying 0.5wt%≤a≤5.5wt%;

[0012] b is the total catalyst content in the applied stream, satisfying 1wt%≤b≤5wt%;

[0013] c is the storage temperature of the applied stream, in °C, and satisfies 20 °C ≤ c ≤ 80 °C;

[0014] d is the storage time of the applied flow stream, in hours;

[0015] The catalyst application stream refers to a material stream that has undergone at least one catalytic cycle and has been enriched through a concentration process to prepare for the next catalytic cycle.

[0016] The inventors found that the increase in oxygen-containing solvent content, catalyst content, storage temperature, and storage time will lead to a decrease in the activity of the metal complex catalyst in the applied flow stream. Taking water as an example, the hydroxyl group in the water molecule will compete with the ligand for complexing, hindering the coordination of the ligand and the stability of the complex catalyst. The high catalyst concentration increases the possibility of the catalyst forming a non-ideal configuration, and the stability of the complexed catalyst and the stability of the ligand will decrease due to the increase in storage temperature or storage time. The present invention can retain the catalyst activity to a great extent by organically combining and regulating the above four dimensions, thereby extending the number of catalyst applications.

[0017] In one embodiment of the present invention, a substrate α / β-unsaturated carbonyl compound is catalytically reacted to obtain a reaction liquid, and the reaction liquid is purified and enriched to obtain a concentrated catalyst stream; wherein the oxygen-containing solvent content in the stream is a, the total catalyst content is b, the storage temperature of the stream is c, and the storage time of the stream is d.

[0018] In one embodiment of the present invention, the oxygen-containing solvent in the set stream is one or more of water and C5-C10 alcohol.

[0019] In one embodiment of the present invention, the catalyst consists of a metal active center and a ligand; preferably, the metal active center is one or more of Ru, Rh, Pd, Pt, Ir, and Co, preferably one or more of Ru, Rh, and Ir; preferably, the ligand is one or more of QuinoxP (2,3-bis(tert-butylmethylphosphino)quinoxaline), BINAP (1,1'-binaphthyl-2,2'-bisdiphenylphosphine), Chiraphos (2,3-bis(diphenylphosphino)butane), Me-DUPHOS (2,2',5,5'-tetramethyl-1,1'-(o-phenylene)diphosphine), NORPHOS (2,3-bis(diphenylphosphino)-bicyclo[2.2.1]hept-5-ene), and BenzP (1,2-bis(tert-butylmethylphosphino)benzene), preferably one or more of QuinoxP, NORPHOS, and Chiraphos. The metal active center and ligand of the asymmetric hydrogenation reaction catalyst are well known in the art. Their selection and dosage have no significant effect on the technical effect of the present invention. Similar effects can be obtained by replacing other selections or dosages.

[0020] Another object of the present invention is to provide a method for improving the catalytic activity of asymmetric hydrogenation reaction catalyst stream.

[0021] A method for improving the catalytic activity of asymmetric hydrogenation reaction catalyst application stream, the method is the above method, the method is used for the asymmetric hydrogenation reaction of unsaturated substrates, preferably for the asymmetric hydrogenation reaction of α / β-unsaturated carbonyl compounds.

[0022] Compared with the prior art, the present invention has the positive effect of significantly improving the activity of the applied catalyst and greatly improving the operation stability of the device. DETAILED DESCRIPTION

[0023] The present invention will be further described in detail below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.

[0024] Main raw materials

[0025] Citral: purity >97%, Wanhua Chemical Group Co., Ltd.

[0026] Neraldehyde: purity> 98%, obtained by distillation of the above-mentioned citral, the distillation method is well known;

[0027] Ruthenium acetylacetonate: purity 99.8%, Aladdin Reagent Co., Ltd.

[0028] Rhodium triacetylacetonate: purity ≥99.99%, Aladdin Reagent Co., Ltd.

[0029] (R)QuinoxP: (R,R)-(-)-2,3-bis(tert-butylmethylphosphino)quinoxaline, purity ≥95%, Merck Group;

[0030] (R)Chiraphos: (2R,3R)-(+)-2,3-bis(diphenylphosphino)butane, purity ≥97%, Aladdin Reagents Co., Ltd.

[0031] Device Information

[0032] 500ml high pressure reactor, Yantai Keli Chemical Equipment Co., Ltd.

[0033] Analytical methods:

[0034] The analytical method for testing conversion and C5-C10 alcohol oxygenated solvents is:

[0035] Gas chromatograph, Agilent 7890B, chromatographic column DB-5 (column length 30m, column inner diameter 0.32mm, liquid film thickness 0.25μm), vaporization chamber temperature 280℃; split ratio 50:1; carrier gas flow rate 1.5ml / min; heating program: maintain at 80℃ for 2min, increase to 280℃ at a rate of 15℃ / min, maintain for 10min, FID detector temperature 300℃.

[0036] The analytical method for testing the selectivity of R-citronellal is as follows: gas chromatograph, Agilent 7890B, chromatographic column BETA-DEX-225 (column length 30m, column inner diameter 0.25mm, liquid film thickness 0.25μm), vaporization chamber temperature 220℃; split ratio 100:1; carrier gas flow rate 1.0ml / min; heating program: maintain at 85℃ for 55min, increase to 130℃ at a rate of 20℃ / min, maintain for 15min, FID detector temperature 300℃.

[0037] The analytical method for testing water content is:

[0038] Gas chromatograph, Agilent 7890B, chromatographic column HP-INNOWAX (column length 60m, column inner diameter 0.53mm, liquid film thickness 1μm), vaporization chamber temperature 200℃; split ratio 10:1; carrier gas flow rate 5ml / min; heating program: maintain at 90℃ for 8min, increase to 220℃ at a rate of 15℃ / min, maintain for 10min, TCD detector temperature 230℃.

[0039] Example 1

[0040] (0.398 g, 0.001 mol) ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 99.1% and the selectivity of R-citronellal was 92.5%.

[0041] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 5.37 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 0.51 wt%, the catalyst content b was 5.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 50°C.

[0042] After 12 hours, the concentrated solution was transferred to a reactor, and then 1000 g of citronellal was added. The nitrogen in the reactor was replaced with H2, and hydrogen was filled to 6 MPa (G). The temperature was increased, and when the temperature in the reactor reached 60°C, it was recorded as 0h. After 8 hours, the substrate conversion rate was tested to be 90.3%, and the R-citronellal selectivity was 92.0%.

[0043] Example 2

[0044] (0.398 g, 0.001 mol) ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 99.7% and the selectivity of R-citronellal was 92.0%.

[0045] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 26.83 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 2.11 wt%, the catalyst content b was 1.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 20°C.

[0046] After 12 hours, the concentrated solution was transferred to the reactor, and then 1000g of citronellal was added, and the nitrogen in the reactor was replaced with H2, and the hydrogen was filled to 6MPa (G), and the temperature was raised. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the substrate conversion rate was tested to be 93.4%, and the R-citronellal selectivity was 92.3%

[0047] Example 3

[0048] (0.398 g, 0.001 mol) of ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) of citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 98.8% and the selectivity of R-citronellal was 93.0%.

[0049] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 13.41 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 5.21 wt%, the catalyst content b was 2.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 80°C.

[0050] After 24 hours, the concentrated solution was transferred to a reactor, and then 1000 g of citronellal was added. The nitrogen in the reactor was replaced with H2, and hydrogen was filled to 6 MPa (G). The temperature was increased, and when the temperature in the reactor reached 60°C, it was recorded as 0h. After 8 hours, the substrate conversion rate was tested to be 87.4%, and the R-citronellal selectivity was 91.4%.

[0051] Example 4

[0052] (0.400 g, 0.001 mol) of rhodium triacetylacetonate and (0.213 g, 0.0005 mol) (R) Chiraphos were put into a reactor, and the air in the reactor was replaced with nitrogen. Then (1000 g, 6.58 mol) of citronellal was added into the reactor, and the nitrogen in the reactor was replaced with H2. The reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 97.7% and the selectivity of R-citronellal was 93.5%.

[0053] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 10.40 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 5.33 wt%, and the catalyst content b was 2.3 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 80°C.

[0054] After 24 hours, the concentrated solution was transferred to the reactor, and then 1000g of citronellal was added, and the nitrogen in the reactor was replaced with H2, and the hydrogen was filled to 6MPa (G), and the temperature was raised. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the substrate conversion rate was tested to be 90.2%, and the selectivity of R-citronellal was 91.4%

[0055] Comparative Example 1

[0056] Compared with Example 1, the difference is that the storage time does not meet the inequality requirement, and the value on the right side of the inequality is 17.

[0057] (0.398 g, 0.001 mol) of ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) of citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 99.0% and the selectivity of R-citronellal was 92.7%.

[0058] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 5.37 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 0.55 wt%, the catalyst content b was 5.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 50°C.

[0059] After 24 hours, the concentrated solution was transferred to a reactor, and then 1000 g of citronellal was added. The nitrogen in the reactor was replaced with H2, and hydrogen was filled to 6 MPa (G). The temperature was increased, and when the temperature in the reactor reached 60°C, it was recorded as 0h. After 8 hours, the substrate conversion rate was tested to be 71.0%, and the R-citronellal selectivity was 90.1%.

[0060] Comparative Example 2

[0061] Compared with Example 2, the difference is that the content of oxygen-containing solvent is too high, which is 6.85%.

[0062] (0.398 g, 0.001 mol) of ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) of citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 99.1% and the selectivity of R-citronellal was 92.0%.

[0063] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to 26.83 g. The concentrated liquid was then transferred into a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 6.85 wt%, the catalyst content b was 1.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 20°C.

[0064] After 12 hours, the concentrated solution was transferred to a reactor, and then 1000 g of citronellal was added. The nitrogen in the reactor was replaced with H2, and hydrogen was filled to 6 MPa (G). The temperature was increased, and when the temperature in the reactor reached 60°C, it was recorded as 0h. After 8 hours, the substrate conversion rate was tested to be 69.5%, and the R-citronellal selectivity was 89.6%.

[0065] Comparative Example 3

[0066] Compared with Example 3, the difference is that the oxygen-containing solvent content is too high at 7.21%, and the storage time does not meet the requirements of the inequality, and the right side of the inequality is 43 hours.

[0067] (0.398 g, 0.001 mol) ruthenium acetylacetonate and (0.167 g, 0.0005 mol) (R) QuinoxP were put into a reactor, the air in the reactor was replaced with nitrogen, and then (1000 g, 6.58 mol) citronellal was added into the reactor, the nitrogen in the reactor was replaced with H2, the reactor was filled with hydrogen to 6 MPa (G), and the temperature was increased. When the temperature in the reactor reached 60°C, it was recorded as 0h. After 8h, the conversion rate was 99.0% and the selectivity of R-citronellal was 93.5%.

[0068] Thereafter, the hydrogen in the kettle was replaced with nitrogen, and the reaction liquid was introduced into a scraper evaporator connected to the reactor, and the catalyst was concentrated at 130°C and 1 kPa (A) to concentrate the reaction liquid to 23.92 g. The concentrated liquid was then transferred to a concentrated liquid storage tank, in which the oxygen-containing solvent content a was 7.21 wt%, the catalyst content b was 1.0 wt%, and the temperature of the concentrated liquid storage tank was adjusted to 20°C.

[0069] After 48 hours, the concentrated solution was transferred to a reactor, and then 1000 g of citronellal was added. The nitrogen in the reactor was replaced with H2, and hydrogen was filled to 6 MPa (G). The temperature was increased, and when the temperature in the reactor reached 60°C, it was recorded as 0h. After 8 hours, the substrate conversion rate was tested to be 46.3%, and the R-citronellal selectivity was 76.9%.

[0070] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A method for improving the activity of asymmetric hydrogenation catalyst, characterized in that: In the method: The parameters of the catalyst application stream should satisfy the following relationship: in: a is the oxygen-containing solvent content in the applied stream, satisfying 0.5wt%≤a≤5.5wt%; b is the total catalyst content in the applied stream, satisfying 1wt%≤b≤5wt%; c is the storage temperature of the applied stream, in °C, and satisfies 20 °C ≤ c ≤ 80 °C; d is the storage time of the applied flow stream, in hours; The catalyst application stream refers to a material stream that has undergone at least one catalytic cycle and has been enriched through a concentration process to prepare for the next catalytic cycle.

2. The method according to claim 1, characterized in that In the method, a substrate α / β-unsaturated carbonyl compound is subjected to a catalytic reaction to obtain a reaction solution, and the reaction solution is purified and enriched to obtain a concentrated catalyst stream; Among them, the oxygen-containing solvent content in the stream is a, the total catalyst content is b, the storage temperature of the stream is c, and the storage time of the stream is d.

3. The method according to claim 1 or 2, characterized in that: The oxygen-containing solvent in the applied flow stream is one or more of water and C5-C10 alcohol.

4. The method according to any one of claims 1 to 3, characterized in that The catalyst is composed of a metal active center and a ligand; Preferably, the metal active center is one or more of Ru, Rh, Pd, Pt, Ir, and Co, preferably one or more of Ru, Rh, and Ir; Preferably, the ligand is one or more of QuinoxP, BINAP, Chiraphos, Me-DUPHOS, NORPHOS, and BenzP, preferably one or more of QuinoxP, NORPHOS, and Chiraphos.

5. Use of a method for improving the catalytic activity of a catalyst stream for asymmetric hydrogenation reaction, the method being the method according to any one of claims 1 to 4, the method being used for asymmetric hydrogenation reaction of unsaturated substrates, preferably for asymmetric hydrogenation reaction of α / β-unsaturated carbonyl compounds.

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