CN112403504A - Nitrogen-sulfur co-doped catalyst and preparation method and application thereof - Google Patents
Nitrogen-sulfur co-doped catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen-sulfur co-doped catalyst and a preparation method and application thereof. According to the invention, the catalyst prepared by loading the noble metal coordinated by the nitrogen species on the carrier prepared by doping the carbon material with the nitrogen and sulfur species is utilized, so that the catalytic hydrogenation reaction activity is effectively improved, and the catalyst has higher hydrogenation selectivity on a biotin intermediate and can be recycled; in addition, the invention introduces a trace amount of alkaline auxiliary agents such as sodium hydroxide, potassium hydroxide and the like into a hydrogenation reaction system for preparing the biotin intermediate, so that the reaction activity can be effectively improved, and the esterification selectivity can be reduced.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nitrogen-sulfur co-doped catalyst and a preparation method and application thereof.
Background
Biotin, also known as vitamin B7, vitamin H, and coenzyme R, is an essential substance for the synthesis of vitamin C, and is an essential nutrient for maintaining the normal growth, development, and health of the body. In recent years, biotin has become one of the most interesting water-soluble vitamins, and has been widely used in the feed industry, the pharmaceutical industry, and the food industry at present.
The molecular formula of biotin is C10H16O3N2S consists of an imidazole ring and a tetrahydrothiophene ring, and an n-pentanoic acid side chain is connected to the thiophene ring, so that the vitamin E is the most complex variety in the production process. The synthesis of the method needs to carry out multi-step reactions, the earliest synthesis method in industry is a lactone-thiolactone synthesis method developed by Roche corporation in 1949, trans-butenedioic acid is taken as a starting material for synthesis, and the improved synthesis method becomes a main method for producing biotin in the world. The main steps of the domestic industrial production comprise bromine addition taking trans-butenedioic acid as an initiator, benzylamine substitution, cyclization, imide synthesis, reduction, lactone synthesis, sulfo-group, side chain addition, catalytic hydrogenation, debenzylation and other reactions, and D-biotin is finally obtained.
In the above catalytic hydrogenation step, the olefinic bond on the cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybut-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole side chain needs to be hydrogenated and saturated, and the 3 rd chiral center is established stereospecifically. In this hydrogenation step, the catalytic hydrogenation catalysts reported in the literature are mostly heterogeneous catalysts, such as palladium/carbon, palladium hydroxide/carbon or nickel catalysts. For example, Isaka et al used nickel-kieselguhr in 1968 for catalytic hydrogenation in methanol. In 1973, Gerecke et al, Roche, Inc., used Raney-Ni as a catalyst. In 1989, McGarrity and Tenud from Lonza used a 5% palladium on carbon catalyst. In the current industrial production, the palladium-based catalyst is more widely applied due to better catalytic hydrogenation performance, but in the actual reaction process, the thioether bond of sulfur on a reaction substrate thiophene ring is easy to break and open under the hydrogenation condition to form a mercaptan structure, and the mercaptan structure is easy to poison and drag after being combined with Pd on the catalyst, so that active metal in the catalyst is lost, the catalyst cannot be recycled, and a large amount of catalyst is wasted.
In the process of industrially synthesizing biotin, olefin on a cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole side chain needs to be subjected to catalytic hydrogenation to further obtain a biotin intermediate so as to saturate the biotin intermediate. The currently used common palladium-carbon catalyst has low hydrogenation selectivity for preparing a target biotin intermediate after completing one-time reaction, and the catalyst cannot be recycled because the catalyst is inactivated due to loss and poisoning of metal palladium, so that the cost of industrial application is greatly increased, and the waste of the catalyst is caused. Therefore, the development of the catalyst which can improve the hydrogenation selectivity of the biotin intermediate in the process of synthesizing biotin and can be recycled has important practical significance.
Disclosure of Invention
An object of the present invention is to solve the existing problems and provide a nitrogen and sulfur co-doped catalyst.
The invention adopts the following technical scheme:
the invention provides a nitrogen and sulfur co-doped catalyst, which has a general formula of M/CxNySz; m is a nitrogen-containing compound modified noble metal; and the CxNySz is a nitrogen and sulfur co-doped carbon carrier.
The invention provides a preparation method of a nitrogen-sulfur co-doped catalyst, which comprises the following steps:
1) preparing a nitrogen-sulfur co-doped carbon carrier: and mixing the carbon material, urea and thiourea, grinding uniformly, calcining in the air atmosphere, cleaning, filtering, and drying to obtain the nitrogen and sulfur co-doped carbon carrier CxNySz.
2) Preparing a precursor solution of the nitrogen-containing compound modified noble metal: and (3) dropwise adding the urea aqueous solution into the precursor solution of the noble metal, stirring and uniformly dispersing to obtain the precursor solution of the nitrogen-containing compound modified noble metal.
3) Preparing a nitrogen-sulfur co-doped catalyst: dripping the precursor solution prepared in the step 2) into the CxNySz aqueous solution prepared in the step 1), stirring for 6-15h, adding an alkali solution to adjust the pH value to 8-9, performing suction filtration, washing, drying, and reducing under the hydrogen condition to obtain the nitrogen-sulfur co-doped catalyst.
Preferably, the mass ratio of the carbon material, the urea and the thiourea in the step 1) is 1: 2-6: 0.5-1.
Preferably, the molar ratio of the urea to the noble metal in the step 2) is (2-4) to 1.
Further preferably, the molar ratio of urea to noble metal in step 2) is 3: 1.
Preferably, the precursor solution of the noble metal in the step 2) is at least one selected from the group consisting of a chloropalladate solution, a palladium chloride solution and a sodium chloropalladite solution.
Preferably, the alkali solution in the step 3) is at least one selected from a sodium hydroxide solution and a potassium hydroxide solution.
Further preferably, the alkali solution in the step 3) is a sodium hydroxide solution.
Preferably, the reduction temperature of the hydrogen gas in the step 3) is 60-100 ℃.
Further preferably, the reduction temperature of the hydrogen condition in the step 3) is 80 ℃.
The third aspect of the invention provides an application of a nitrogen and sulfur co-doped catalyst in preparation of a biotin intermediate by hydrogenation, which comprises the following steps: dissolving a substrate in an alcohol solvent, adding a catalyst and an auxiliary agent, replacing hydrogen, and stirring for reaction in a hydrogen atmosphere; the catalyst is as provided in the above first aspect or obtained by any of the above second aspect preparation methods.
Preferably, the substrate is cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybut-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole.
Preferably, the auxiliary agent is at least one selected from sodium hydroxide and potassium hydroxide.
Further preferably, the auxiliary agent is sodium hydroxide.
Preferably, the molar ratio of the substrate to the auxiliary agent is (10-60) to 1.
Advantageous effects
(1) The invention utilizes the carrier prepared by doping the carbon material with nitrogen and sulfur species and then loads the catalyst prepared by the noble metal coordinated by the nitrogen species, the reaction for preparing the biotin intermediate by hydrogenation can obviously improve the reaction activity and the hydrogenation selectivity, and the hydrogenation selectivity of the biotin intermediate prepared can reach more than 96 percent.
(2) The catalyst can effectively prevent the poisoning and loss of noble metals in the catalyst, improve the reuse frequency of catalytic reaction and effectively inhibit the isomerization of the reaction.
(3) The invention introduces a trace amount of alkaline auxiliary agents such as sodium hydroxide, potassium hydroxide and the like into a reaction system for preparing the biotin intermediate by hydrogenation, can effectively improve the reaction activity, reduce the esterification selectivity and successfully control the selectivity of the esterification product to be less than 1 percent.
Drawings
FIG. 1 is a high resolution transmission electron microscope image of the nitrogen and sulfur co-doped catalyst of the present invention.
FIG. 2 is a reaction formula for preparing a biotin intermediate by catalytic hydrogenation of a nitrogen-sulfur co-doped catalyst of the invention.
Detailed Description
The technical solutions of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a nitrogen and sulfur co-doped catalyst, which has a general formula of M/CxNySz; wherein M is a nitrogen-containing compound modified noble metal, and CxNySz is a nitrogen-sulfur co-doped carbon carrier.
In the invention, the nitrogen and sulfur co-doped catalyst has a general formula of M/CxNySz; wherein M is a nitrogen-modified noble metal, and CxNySz is a nitrogen-sulfur co-doped carbon carrier.
The invention provides a preparation method of a nitrogen-sulfur co-doped catalyst, which comprises the following steps:
1) preparing a nitrogen-sulfur co-doped carbon carrier: and mixing the carbon material, urea and thiourea, grinding uniformly, calcining in the air atmosphere, cleaning, filtering, and drying to obtain the nitrogen and sulfur co-doped carbon carrier CxNySz.
2) Preparing a precursor solution of the nitrogen-containing compound modified noble metal: and (3) dropwise adding the urea aqueous solution into the precursor solution of the noble metal, stirring and uniformly dispersing to obtain the precursor solution of the nitrogen-containing compound modified noble metal.
3) Preparing a nitrogen-sulfur co-doped catalyst: dripping the precursor solution prepared in the step 2) into the CxNySz aqueous solution prepared in the step 1), stirring for 6-15h, adding an alkali solution to adjust the pH value to 8-9, performing suction filtration, washing, drying, and reducing under the hydrogen condition to obtain the nitrogen-sulfur co-doped catalyst. FIG. 1 is a high resolution transmission electron microscope image of the nitrogen and sulfur co-doped catalyst of the present invention.
In the embodiment of the invention, the mass ratio of the carbon material, the urea and the thiourea in the step 1) is 1 to (2-6) to (0.5-1).
In the embodiment of the invention, the molar ratio of urea to noble metal in the step 2) is (2-4) to 1; preferably, the molar ratio of urea to noble metal in step 2) is 3: 1.
In the embodiment of the present invention, the precursor solution of the noble metal in step 2) may be selected from one or more of a chloropalladate solution, a palladium chloride solution, and a sodium chloropalladite solution; in a specific embodiment, the precursor solution of the noble metal is a chloropalladate solution.
In the embodiment of the present invention, the alkali solution in step 3) may be selected from one or more of a sodium hydroxide solution and a potassium hydroxide solution; preferably, the alkali solution is a sodium hydroxide solution.
In the embodiment of the invention, the reduction temperature of the hydrogen in the step 3) is 60-100 ℃; preferably, the reduction temperature under hydrogen conditions is 80 ℃.
The invention also provides an application of the nitrogen-sulfur co-doped catalyst in preparation of a biotin intermediate by hydrogenation, which comprises the following steps: dissolving a substrate in an alcohol solvent, adding a catalyst and an auxiliary agent, replacing hydrogen, and stirring for reaction in a hydrogen atmosphere; the catalyst is the catalyst as provided in the above first aspect or the catalyst obtained by the production method of any one of the above second aspects.
In the present example, the substrate was cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybut-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole. FIG. 2 is a reaction formula for preparing a biotin intermediate by catalytic hydrogenation of a nitrogen-sulfur co-doped catalyst of the invention.
In the embodiment of the present invention, the auxiliary may be selected from one or more of sodium hydroxide and potassium hydroxide; preferably, the adjuvant is sodium hydroxide.
In the embodiment of the invention, the molar ratio of the substrate to the auxiliary agent is (10-60) to 1.
Example 1
1-1 preparation of nitrogen and sulfur co-doped carbon carrier
1g of activated carbon, 5.5g of urea and 0.5g of thiourea are mixed and ground uniformly, the mixture is put into a crucible and sealed by aluminum foil paper, the crucible is placed in a muffle furnace to be calcined for 4 hours at 550 ℃ under the air atmosphere, the heating rate is 5 ℃/min, the mixture is washed by ultrapure water for 3 times, and then is filtered and dried to obtain the nitrogen and sulfur co-doped carbon carrier for later use.
1-2 preparing precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladic acid aqueous solution to 100mL by using deionized water, adding urea to enable the molar ratio of the urea to the Pd to be (2-4) to 1, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain a precursor solution of the nitrogen-containing compound modified palladium for later use.
1-3 preparation of nitrogen and sulfur co-doped catalyst
Adding 1g of nitrogen-sulfur co-doped carbon carrier into 100mL of deionized water for uniform dispersion, slowly dropwise adding 100mL of nitrogen-containing compound modified palladium precursor solution, stirring for 6-15 hours, adding 1mol/L of sodium hydroxide aqueous solution to adjust the pH value to 8-9, performing suction filtration, washing with deionized water for 3 times, drying in a drying oven at 100 ℃, and reducing in a tubular furnace at 60-100 ℃ for 2 hours in a hydrogen atmosphere to obtain the nitrogen-sulfur co-doped catalyst, wherein the active component is nitrogen-modified Pd, and the carrier is nitrogen-sulfur co-doped carbon.
1-4 catalytic hydrogenation reaction
Adding 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of nitrogen-sulfur co-doped catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating for three times, stirring and reacting for 5 hours at 60-100 ℃ under the hydrogen atmosphere of 2MPa, filtering reaction liquid, sampling and analyzing filtrate.
After the filter cake is washed by methanol and is drained, 50mL of methanol is used for washing and is transferred into a high-pressure reactor, 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole is added into the high-pressure reactor for first application, and the application steps are repeated for 7 times.
Table 1 shows the experimental results of the catalytic hydrogenation reaction of the catalyst of the present invention applied for 7 times. It can be seen that the catalyst of the invention has a high conversion rate of the biotin intermediate obtained by hydrogenation, which is more than 97%, and the hydrogenation selectivity of the biotin intermediate is also kept more than 95% after repeated application for 7 times; the selectivity of the esterification product in the reaction 1 time is only 0.6 percent, the esterification selectivity is not obviously improved along with the increase of the repeated application times, and the esterification selectivity is not more than 2.0 percent; and isomerization is effectively inhibited within 2.0 percent.
TABLE 1 data of the results of the catalytic hydrogenation reaction using the catalyst of the present invention for 7 applications
| Number of times | Conv. | Sel. (hydrogenation of biotin intermediate) | Sel. (esterification) | Sel. (isomerism) |
| Reaction 1 time | 99.2％ | 96.3％ | 0.6％ | 1.6％ |
| Apply it for 1 time | 99.1％ | 96.1％ | 1.0％ | 1.6％ |
| Apply it for 2 times | 98.7％ | 96.0％ | 1.0％ | 1.4％ |
| Apply it 3 times | 99.0％ | 95.1％ | 2.0％ | 1.5％ |
| Apply it 4 times | 98.8％ | 95.2％ | 1.9％ | 1.5％ |
| Apply it for 5 times | 100％ | 95.9％ | 1.4％ | 1.4％ |
| Apply it for 6 times | 99.5％ | 95.1％ | 1.9％ | 1.6％ |
| Apply it for 7 times | 97.1％ | 95.8％ | 1.6％ | 1.4％ |
Example 2
1-1 preparation of nitrogen and sulfur co-doped carbon carrier
Mixing and grinding different amounts of activated carbon, urea and thiourea uniformly to form test groups 1-4, respectively filling the test groups into crucibles, sealing the crucibles with aluminum foil paper, calcining the crucibles for 4 hours at 550 ℃ in a muffle furnace under air atmosphere at the heating rate of 5 ℃/min, washing the crucibles for 3 times with ultrapure water, filtering and drying the calcinations to obtain the nitrogen and sulfur co-doped carbon carrier for later use. 1-2 preparing precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladate acid aqueous solution to 100mL by using deionized water, then adding 0.0846g of urea to ensure that the molar ratio of the urea to the Pd is 3: 1, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain a precursor solution of the nitrogen-containing compound modified palladium for later use.
1-3 preparation of nitrogen and sulfur co-doped catalyst
Respectively adding 4 groups of 1g nitrogen-sulfur co-doped carbon carriers into 100mL of deionized water for uniform dispersion, slowly dropwise adding 100mL of nitrogen-containing compound modified palladium precursor solution, stirring for 6-15 hours, adding 1mol/L sodium hydroxide aqueous solution to adjust the pH value to 8-9, performing suction filtration, washing for 3 times by using deionized water, then placing in a 100 ℃ drying oven for drying, and then placing in a tubular furnace for reduction for 2 hours under the hydrogen atmosphere at 80 ℃ to obtain 4 groups of nitrogen-sulfur co-doped catalysts.
1-4 catalytic hydrogenation reaction
And (3) respectively taking 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutane-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of nitrogen-sulfur co-doped catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating for three times, stirring and reacting for 5 hours at 60-100 ℃ in a hydrogen atmosphere of 2MPa, filtering reaction liquid, and sampling and analyzing filtrate.
Table 2 shows the experimental result data of catalytic hydrogenation reaction performed by using different mass ratios of activated carbon, urea and thiourea to prepare the catalyst of the present invention, and it can be seen that when the mass ratio of urea is 2-6 times of that of activated carbon, the conversion rate of catalytic hydrogenation reaction can reach more than 99%, the hydrogenation selectivity to the biotin intermediate can reach more than 96%, the esterification selectivity is less than 1.0%, and the isomerization is less than 2.0%; when the mass of the selected thiourea is 0.5-1 times of that of the active carbon, the conversion rate of catalytic hydrogenation reaction can reach more than 99%, the hydrogenation selectivity on a biotin intermediate can reach more than 96%, the esterification selectivity is less than 1.0%, and the isomerization is less than 2%.
TABLE 2 Experimental data for catalytic hydrogenation of catalysts prepared with different mass ratios of activated carbon, urea and thiourea
Example 3
1-1 preparation of nitrogen and sulfur co-doped carbon carrier
Respectively taking 3 groups of 1g of activated carbon, 5.5g of urea and 0.5g of thiourea, mixing and grinding uniformly to form test groups 5-7, respectively filling the test groups into crucibles, sealing the crucibles with aluminum foil paper, calcining the crucibles for 4 hours at 550 ℃ in a muffle furnace under the air atmosphere, wherein the heating rate is 5 ℃/min, washing the crucibles for 3 times with ultrapure water, filtering, and drying to obtain the nitrogen-sulfur co-doped carbon carrier for later use.
1-2 preparing precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladate acid aqueous solution to 100mL by using deionized water, then adding 0.0846g of urea to ensure that the molar ratio of the urea to the Pd is 3: 1, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain a precursor solution of the nitrogen-containing compound modified palladium for later use.
1-3 preparation of nitrogen and sulfur co-doped catalyst
Respectively adding 3 groups of 1g of nitrogen-sulfur co-doped carbon carriers into 100mL of deionized water for uniform dispersion, slowly dropwise adding 100mL of nitrogen-containing compound modified palladium precursor solution, stirring for 6-15 hours, adding 1mol/L of sodium hydroxide aqueous solution for regulating the pH value, wherein the pH value of a test group 7 is not regulated by adding the sodium hydroxide aqueous solution, the pH value of a test group 8 is regulated to 8-9, the pH value of a test group 9 is regulated to 10, performing suction filtration, washing for 3 times by using the deionized water, drying in a drying oven at 100 ℃, and reducing in a tubular furnace for 2 hours under the hydrogen atmosphere at 80 ℃ to obtain 3 groups of nitrogen-sulfur co-doped catalysts.
1-4 catalytic hydrogenation reaction
And 3 groups of test groups are respectively prepared by adding 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutane-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of nitrogen-sulfur co-doped catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating for three times, stirring and reacting for 5 hours at 60-100 ℃ and 2MPa in a hydrogen atmosphere, filtering reaction liquid, and sampling and analyzing filtrate.
Table 3 shows the experimental result data of the catalytic hydrogenation reaction performed by the catalyst prepared by adjusting different pH values with the aqueous alkali, and it can be seen that when the pH is adjusted to 8-9, which is the optimal range, the conversion rate can reach 100%, the hydrogenation selectivity for preparing the biotin intermediate can reach more than 96%, the esterification selectivity is less than 1%, and the isomerization is only 1.6%.
TABLE 3 Experimental results data for preparing catalysts for catalytic hydrogenation reaction by adjusting different pH values with alkali solution
Example 4
1-1 preparation of nitrogen and sulfur co-doped carbon carrier
1g of activated carbon, 5.5g of urea and 0.5g of thiourea are mixed and ground uniformly, the mixture is put into a crucible and sealed by aluminum foil paper, the crucible is placed in a muffle furnace to be calcined for 4 hours at 550 ℃ under the air atmosphere, the heating rate is 5 ℃/min, the mixture is washed by ultrapure water for 3 times, and then is filtered and dried to obtain the nitrogen and sulfur co-doped carbon carrier for later use.
1-2 preparing precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladate acid aqueous solution to 100mL by using deionized water, then adding 0.0846g of urea to ensure that the molar ratio of the urea to the Pd is 3: 1, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain a precursor solution of the nitrogen-containing compound modified palladium for later use.
1-3 preparation of nitrogen and sulfur co-doped catalyst
Adding 1g of nitrogen-sulfur co-doped carbon carrier into 100mL of deionized water for uniform dispersion, slowly dropwise adding 100mL of palladium precursor solution modified by nitrogen-containing compounds, stirring for 6-15 hours, adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value to 8-9, performing suction filtration, washing for 3 times by using deionized water, drying in a drying oven at 100 ℃, and reducing in a tubular furnace at 60-100 ℃ for 2 hours to obtain the nitrogen-sulfur co-doped catalyst.
1-4 catalytic hydrogenation reaction
Taking 3 groups of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutane-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole as a substrate, potassium hydroxide as an auxiliary agent, 50mL of methanol and 0.2g of nitrogen-sulfur co-doped catalyst, adding the mixture into a high-pressure reactor, wherein the molar ratio of the substrate to the auxiliary agent is (10-60) to 1, forming a test group of 8-10, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating for three times, stirring and reacting for 5 hours at 60-100 ℃ and 2MPa in a hydrogen atmosphere, filtering reaction liquid, and sampling and analyzing filtrate.
Table 4 shows the experimental result data of the catalyst of the present invention in the catalytic hydrogenation reaction system with different molar ratios of the substrate and the auxiliary agent, and it can be seen that when the catalyst of the present invention is used to prepare the biotin intermediate through catalytic hydrogenation of the substrate, the hydrogenation reaction effect for preparing the biotin intermediate is good, the conversion rate can reach more than 99%, the hydrogenation selectivity for the biotin intermediate can reach more than 96%, the esterification selectivity is less than 1.0%, and the isomerization is less than 2.0%, when the molar ratio of the substrate to the potassium hydroxide auxiliary agent is in the range of (10-60) to 1.
TABLE 4 data of experimental results of the catalyst of the present invention in catalytic hydrogenation reaction systems with different molar ratios of substrate to auxiliary
Comparative example 1
1-1 preparation of palladium-carbon catalyst
Respectively dripping 3 groups of chloropalladate precursor solutions into activated carbon dispersed by ultrapure water to form comparison groups 1, 2 and 3, soaking and stirring for 12 hours, adjusting the pH value of the comparison group 2 to 8-9 by using a 1mol/L NaOH aqueous solution, adjusting the pH value of the comparison group 3 to 10, not adjusting the pH value of the comparison group 1, performing suction filtration, washing for 3 times by using deionized water, drying in a drying box at 100 ℃, and reducing in a tubular furnace for 2 hours at 60-100 ℃ in a hydrogen atmosphere to obtain 3 groups of palladium-carbon catalysts.
1-2 catalytic hydrogenation reaction
And 3 groups of comparison groups are respectively prepared by adding 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of palladium-carbon catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating for three times, stirring and reacting for 5 hours in a hydrogen atmosphere at 60-100 ℃ and 2MPa, filtering reaction liquid after the reaction is finished, and sampling and analyzing filtrate.
Table 5 shows the experimental result data of the catalytic hydrogenation reaction performed by the palladium-carbon catalyst, and it can be seen that the palladium-carbon catalyst prepared without adjusting the pH value has very high selectivity for esterification in the catalytic hydrogenation reaction, and the hydrogenation selectivity of the target product biotin intermediate is very low; the palladium-carbon catalyst prepared by adjusting the pH value with NaOH aqueous solution can improve the hydrogenation selectivity of the biotin intermediate and reduce esterification reaction.
In addition, although the pH is adjusted to 8-9 in the catalyst preparation process, the selectivity of the hydrogenation reaction can be improved and the esterification reaction can be inhibited in a fixed degree, compared with the hydrogenation reaction of the catalyst prepared by the invention, the conversion rate of the palladium-carbon catalyst which is not treated by urea and thiourea on the catalytic hydrogenation reaction and the hydrogenation selectivity of a biotin intermediate are still generally lower, the esterification selectivity is higher, and the obtained product is not suitable for synthesizing biotin.
TABLE 5 data of the results of the catalytic hydrogenation reaction with palladium on carbon catalyst
Comparative example 2
1-1 preparation of precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladate acid aqueous solution to 100mL by using deionized water, then adding 0.0846g of urea, wherein the molar ratio of the urea to the Pd is 3: 1, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain the precursor solution of the nitrogen-containing compound modified palladium.
1-2 preparation of the catalyst
Slowly dropping 100mL of palladium precursor solution modified by nitrogen-containing compound into the activated carbon dispersed by ultrapure water, stirring for 6-15h, adding 1mol/L sodium hydroxide aqueous solution to adjust the pH value to 8-9, performing suction filtration, washing for 3 times by deionized water, placing in a drying oven at 100 ℃ for drying overnight, and then placing in a tubular furnace to reduce for 2h under the atmosphere of 80 ℃ hydrogen to obtain the catalyst.
1-3 catalytic hydrogenation reaction
Adding 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of palladium-carbon catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating three times, stirring and reacting for 5 hours at 60-100 ℃ in a 2MPa hydrogen atmosphere, filtering the reaction solution, and sampling and analyzing the filtrate. After the filter cake is washed by methanol and drained, the filter cake is washed by 50mL of methanol in full volume and transferred into a high-pressure reactor, and 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutyl-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole is added into the high-pressure reactor for one-time use.
Table 6 shows the experimental result data of the catalytic hydrogenation reaction of the catalyst prepared from the precursor solution of palladium modified by nitrogen-containing compound, which shows that compared with the catalyst of the present invention, the catalyst is poisoned and inactivated after 1 reaction, and can not be reused.
TABLE 6 Experimental result data of catalytic hydrogenation reaction of catalyst prepared from palladium precursor solution modified by nitrogen-containing compound
| Number of reaction times | Conv. | Sel. (hydrogenation of biotin intermediate) | Sel. (esterification) | Sel. (isomerism) |
| Reaction 1 time | 100％ | 96.1％ | 0.7％ | 2.2％ |
| Is used once | 20.5％ | - | - | - |
Comparative examples 3 to 8
Comparative example 3
1-1 preparation of Nitrogen-doped carbon Supports
1g of active carbon and 1g of urea are mixed and ground uniformly, and the mixture is put into a crucible and sealed by aluminum foil paper. Calcining at 550 deg.C for 4 hr in a muffle furnace under air atmosphere at a heating rate of 5 deg.C/min. And washing the carbon carrier by ultrapure water for three times, and then carrying out suction filtration and drying to obtain the nitrogen-doped carbon carrier for later use.
1-2 preparing precursor solution of palladium modified by nitrogen-containing compound
Diluting 2.5mL of 20g/1000mL chloropalladic acid aqueous solution to 100mL by using deionized water, then adding 0.0846g of urea with the molar weight being 3 times of Pd, stirring for 1 hour at normal temperature, and uniformly dispersing to obtain a precursor solution of the palladium modified by the nitrogen-containing compound for later use.
1-3 preparation of the catalyst
Adding 1g of nitrogen-doped carbon carrier into 100mL of deionized water for uniform dispersion, then slowly dropwise adding 100mL of palladium precursor solution modified by nitrogen-containing compounds, stirring for 6-15h, adding 1mol/L of sodium hydroxide aqueous solution to adjust the pH value to 8-9, performing suction filtration, washing for 3 times with deionized water, drying in a drying oven at 100 ℃, and then placing in a tubular furnace for hydrogen reduction at 60-100 ℃ for 2h to obtain the catalyst.
1-4 catalytic hydrogenation reaction
Adding 5g of cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybutane-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole, 50mL of methanol, 0.2g of catalyst and 0.016g of sodium hydroxide into a high-pressure reactor, replacing air with nitrogen, replacing nitrogen with hydrogen, circulating three times, stirring and reacting for 5 hours at 60-100 ℃ and 2MPa in a hydrogen atmosphere, filtering the reaction solution, and sampling and analyzing the filtrate.
Comparative example 4
Compared with comparative example 3, the amount of urea used in step 1-1 was changed to 2g, and the remaining steps were the same as in comparative example 3.
Comparative example 5
Compared with the comparative example 3, the amount of urea used in the step 1-1 was changed to 3g, and the remaining steps were the same as the comparative example 3.
Comparative example 6
Compared with comparative example 3, the amount of urea used in step 1-1 was changed to 4g, and the remaining steps were the same as in comparative example 3.
Comparative example 7
Compared with comparative example 3, the amount of urea used in step 1-1 was changed to 5g, and the remaining steps were the same as in comparative example 3.
Comparative example 8
Compared with comparative example 3, the amount of urea used in step 1-1 was changed to 6g, and the remaining steps were the same as in comparative example 3.
TABLE 7 Experimental results data for the preparation of biotin intermediates by catalytic hydrogenation in different catalysts
As can be seen from the data of the catalytic hydrogenation experimental results of comparative examples 3 to 8 in table 7, compared with the catalyst of the present invention, the hydrogenation selectivity of the catalyst prepared by using the nitrogen-doped carbon carrier formed by modifying activated carbon with urea is not more than 87% when the catalyst is used for preparing the biotin intermediate through hydrogenation, while the hydrogenation selectivity of the catalyst prepared by using the nitrogen-sulfur co-doped carbon carrier of the present invention for preparing the biotin intermediate through catalytic hydrogenation can reach more than 96%, which is significantly improved.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. The nitrogen-sulfur co-doped catalyst is characterized in that the general formula of the catalyst is M/CxNySz; m is a nitrogen-containing compound modified noble metal; and the CxNySz is a nitrogen and sulfur co-doped carbon carrier.
2. The preparation method of the nitrogen-sulfur co-doped catalyst is characterized by comprising the following steps of:
1) preparing a nitrogen-sulfur co-doped carbon carrier: and mixing the carbon material, urea and thiourea, grinding uniformly, calcining in the air atmosphere, cleaning, filtering, and drying to obtain the nitrogen and sulfur co-doped carbon carrier CxNySz.
2) Preparing a precursor solution of the nitrogen-containing compound modified noble metal: and (3) dropwise adding the urea aqueous solution into the precursor solution of the noble metal, stirring and uniformly dispersing to obtain the precursor solution of the nitrogen-containing compound modified noble metal.
3) Preparing a nitrogen-sulfur co-doped catalyst: dripping the precursor solution prepared in the step 2) into the CxNySz aqueous solution prepared in the step 1), stirring for 6-15h, adding an alkali solution to adjust the pH value to 8-9, performing suction filtration, washing, drying, and reducing under the hydrogen condition to obtain the nitrogen-sulfur co-doped catalyst.
3. The preparation method according to claim 2, wherein the mass ratio of the carbon material, the urea and the thiourea in the step 1) is 1: 2-6: 0.5-1.
4. The preparation method of claim 2, wherein the molar ratio of the urea to the noble metal in the step 2) is (2-4) to 1.
5. The production method according to claim 2, wherein the alkali solution in the step 3) is at least one selected from a sodium hydroxide solution and a potassium hydroxide solution.
6. The method according to claim 2, wherein the reduction temperature of the hydrogen gas in the step 3) is 60 to 100 ℃.
7. The application of the nitrogen-sulfur co-doped catalyst in the preparation of the biotin intermediate through hydrogenation is characterized by comprising the following steps of: dissolving a substrate in an alcohol solvent, adding a catalyst and an auxiliary agent, replacing hydrogen, and stirring for reaction in a hydrogen atmosphere; the catalyst is the catalyst according to claim 1 or the catalyst obtained by the production method according to any one of claims 2 to 6.
8. Use according to claim 7, wherein the substrate is cis-2-oxo-1, 3-dibenzyl-4- (4-carboxybut-1-ene) hexahydro-1H-thieno [3, 4-d ] imidazole.
9. Use according to claim 7, wherein the adjuvant is selected from at least one of sodium hydroxide and potassium hydroxide.
10. The use according to claim 7, wherein the molar ratio of the substrate to the adjuvant is (10-60) to 1.
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