CN113788737B

CN113788737B - Three-bond partial hydrogenation method and catalyst thereof

Info

Publication number: CN113788737B
Application number: CN202110983019.2A
Authority: CN
Inventors: 黄文学; 闫化莲; 马宏宇; 薛勇勇; 孙媛媛; 马文成; 王永军; 黎源
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2021-08-25
Filing date: 2021-08-25
Publication date: 2024-06-25
Anticipated expiration: 2041-08-25
Also published as: CN113788737A

Abstract

The invention provides a three-bond partial hydrogenation method and a catalyst thereof. The catalyst comprises a carrier, main catalyst metal palladium loaded on the carrier, auxiliary metal and poisoning agent; the carrier is calcium carbonate, barium sulfate, aluminum oxide and silicon oxide; the auxiliary metal is tungsten, molybdenum and manganese metal simple substance; the poisoning auxiliary agent is lead salt, zinc salt and chromium salt. The catalyst in the hydrogenation method has excellent partial hydrogenation activity and selectivity, and can realize the partial hydrogenation of the carbon-carbon triple bond with high yield to obtain olefin products. In the reaction process, carbon dioxide and a small amount of alcohol amine are introduced into the reaction system, so that the occurrence of dimerization side reaction of the alkynol serving as a raw material is reduced, and the selectivity of partial hydrogenation reaction is further improved.

Description

Three-bond partial hydrogenation method and catalyst thereof

Technical Field

The invention belongs to the fields of fine chemical synthesis and catalyst preparation, and in particular relates to a three-bond partial hydrogenation method and a catalyst thereof.

Background

The triple bond selective hydrogenation reaction is widely applied to various chemical fields, whether the chemical fields are bulk chemicals or fine chemicals. For example, in the refining, the ethylene obtained by cracking generally contains a small amount of acetylene, and acetylene has a very strong poisoning effect on the polyethylene catalyst, so that the acetylene in the ethylene needs to be purified before polymerization, and a method for partially hydrogenating the acetylene to obtain ethylene is widely adopted at present. In the field of fine chemicals, allyl alcohol is a widely occurring building block such as allyl salicylate, allyl cinnamate, allyl caproate, leaf alcohol, linalool, dihydromyrcenol, etc., all of which have an allyl structure in their molecular structure, and one of the most common methods to obtain such an allyl structure is the partial hydrogenation of the C-C triple bond of the propargyl precursor.

In the last 50 th century, the Chemie lindlar of the Roche company adsorbed palladium on a certain carrier, such as calcium carbonate or barium sulfate, and a small amount of poisoning agent, such as lead acetate, quinoline, etc. was added to further poison the hydrogenation activity of palladium metal and promote the selectivity thereof. Lindla catalysts have achieved great success and have found extremely wide application in both laboratory and industrial settings. Since the invention of lindla catalysts, numerous researchers have come from the front and behind, exploring the mechanism of partial hydrogenation thereof, and continuously improving this type of catalyst.

For example, patent CN1311179a adopts a palladium catalyst supported on a fixed bed, and 10-2000ppm of CO is added into the hydrogenation gas, so that the catalyst is very suitable for partial hydrogenation of monosubstituted alkyne, and the selectivity of the target product is more than 93%. Patent CN101616733a adopts a regular catalyst, metallic palladium and zinc oxide are loaded on metal fiber, quinoline is used as poisoning agent, and catalytic partial hydrogenation obtains better reaction conversion rate and selectivity. Patent CN101869845A uses calcium carbonate as carrier, palladium as active component, mn, bi or Zn as poisoning agent, and adsorption of palladium on carrier, then filtering, then reducing to obtain the catalyst, and said catalyst possesses high activity and selectivity (97%) for selective hydrogenation of isophytol. The patent CN104394988 adopts calcium carbonate with the average grain diameter larger than 10Pm as a carrier and lead as a poisoning agent, and when the average grain diameter of the carrier is larger than 10Pm, the selectivity of hydrogenation products is obviously improved. Patent CN110573248 uses zinc oxide, cerium oxide, etc. as carrier materials, and does not use calcium carbonate carrier, the prepared catalyst shows improved activity and selectivity in partial hydrogenation reaction.

In summary, although lindera catalysts have achieved great success, the current lindera catalysts still cannot achieve extremely high selectivity; in practical production applications, in order to ensure stable selectivity and activity of the lindlar catalyst, different poisoning agents or auxiliary agents such as pyridine, quinoline and the like are generally required to be added, and the different poisoning agents or auxiliary agents bring difficulty to separation of partial hydrogenation products, and a small amount of residues influence the product quality, especially essence and perfume products.

In the partial hydrogenation reaction, palladium metal can catalyze alkynol substrate to dehydrodimerization to obtain byproducts of high-boiling-point dialkynol; the addition of basic poisoning agents such as quinoline can further promote this side reaction. Therefore, a novel lindlar catalyst still needs to be developed at present, so that the selectivity and activity of the catalyst are further improved, and the cost of the catalyst is reduced; meanwhile, a new poisoning agent needs to be searched, the alkalinity of the poisoning agent is weaker than that of pyridine and quinoline, and the promotion effect on the alkynol dimerization side reaction is reduced; in addition, the method also considers how to further weaken the alkalinity of the reaction system and reduce the side reaction of alkynol dimerization.

Disclosure of Invention

The invention aims to provide a three-bond partial hydrogenation method and a catalyst thereof, which solve the problems of more dimerization side reactions and urgent improvement of reaction selectivity of the existing partial hydrogenation reaction substrate.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

a triple bond partial hydrogenation process for partially hydrogenating alkyne feedstock to produce alkene, wherein the hydrogenation process employs an alcohol amine in combination with a palladium-containing catalyst to achieve a controlled hydrogenation reaction.

In the invention, the palladium-containing catalyst consists of the following components: (I) a carrier, 84.5 to 98.8wt%; (II) 1-10wt% of main catalyst metal palladium; (III) 0.1 to 0.5 weight percent of additive metal; (IV) poisoning agent, 0.1-5.0wt%; wherein the carrier is one or more of calcium carbonate, barium sulfate, aluminum oxide and silicon oxide; the auxiliary metal is one or more of elemental tungsten, elemental molybdenum and elemental manganese; the poisoning agent is one or more of lead salt, zinc salt and chromium salt; the percentages being based on the total mass of the catalyst. The selected auxiliary agents such as metal manganese, molybdenum, tungsten and the like have better adsorption effect on carbon-carbon triple bonds, and can enhance the selective adsorption of the catalyst on alkynol substrates, thereby improving the selectivity of the catalyst.

In the invention, the alcohol amine is one or more of triethanolamine, diethanolamine, diisopropanolamine and triisopropanolamine, and the dosage of the alcohol amine is 0.05-0.5 wt% of the mass of the substrate. The alcohol amine has certain coordination capacity, can be weakly coordinated with palladium metal, adjusts palladium hydrogenation selectivity, has weak self acidity, and does not promote palladium to catalyze alkynol coupling side reaction; in addition, the alcohol amine has hydroxyl and amine functional groups, is often used as a carbon dioxide adsorbent in industry, can promote the dissolution of carbon dioxide in a reaction liquid phase, and further reduces the alkalinity of the system.

In the invention, the hydrogenation method is a batch reaction or a continuous reaction; preferably, the reaction time of the batch reaction is 2 to 6 hours; the temperature of the reaction is 40-80 ℃; the pressure of the reaction gas is 0.2-2.0 MPa, the partial pressure of carbon dioxide is 1-5%, the rest is hydrogen, and the gas pressure is kept stable in the reaction process; the catalyst is used in an amount of 0.5 to 2.0wt% relative to the mass of the substrate. Carbon dioxide is acid gas, so that the alkalinity of the whole reaction system can be reduced, and the dehydrogenation coupling side reaction of alkynol substrates can be reduced.

In the invention, the partial hydrogenation reaction can be carried out without adding or adding a solvent; if a solvent is added, the solvent is one or more of methanol, ethanol, isopropanol, acetone and tetrahydrofuran, preferably ethanol.

In one embodiment, the process for partially hydrogenating an alkyne feedstock to produce an alkene comprises the steps of:

(1) Under the nitrogen atmosphere, alkyne raw material, solvent, alcohol amine and catalyst are fed into a reaction kettle at one time;

(2) Replacing nitrogen with hydrogen, and then introducing a mixed gas of carbon dioxide and hydrogen;

(3) The reaction liquid reacts under the rapid stirring, and alkyne raw material is selectively hydrogenated to obtain alkene.

It is another object of the present invention to provide a method for preparing the catalyst.

A method of preparing the catalyst, the method comprising the steps of:

SS1: impregnating the carrier material in palladium salt and auxiliary metal salt solution, and calcining and reducing to obtain a catalyst precursor;

SS2: the catalyst precursor is immersed in a poisoning agent solvent, and catalyst poisoning and modification are carried out in the presence of a reducing agent to a target catalyst.

In the invention, the palladium salt in the SS1 is one or more of palladium chloride, palladium nitrate, palladium acetate and dihydro-tetrachloropalladium acid.

In the invention, the auxiliary metal in the SS1 is one or more of molybdenum nitrate, molybdenum acetate, manganese nitrate and tungsten tetrachloride.

In the invention, the poisoning agent in the SS2 is one or more of lead acetate, zinc oxide, zinc acetate, zinc chloride and cadmium acetate.

It is a further object of the present invention to provide the use of a triple bond partial hydrogenation process.

Use of a triple bond partial hydrogenation process for the partial hydrogenation of an alkyne feedstock to produce an alkene, preferably an alkyne feedstock being any one of methylbutynol, methylpentanynol, dehydrolinalool, dihydrodehydrolinalool, dehydronerolidol, 1, 4-butynediol and dehydroisophytol.

In the present invention, the pressures are gauge pressures unless otherwise specified.

Compared with the prior art, the technical scheme of the invention has the following positive effects:

1. The preparation process of the catalyst is relatively simple, the operation is convenient, the kilogram-level catalyst is easy to prepare in an amplified manner, and the catalyst has a good application prospect.

2. The metal tungsten, manganese, molybdenum simple substance and the like which have strong adsorption effect on the carbon-carbon triple bond are used as catalyst metal auxiliary agents, so that the selective adsorption of the catalyst on the carbon-carbon triple bond substrate is enhanced, and the selectivity of partial hydrogenation reaction is improved.

3. The catalyst has good performance and wide substrate application range, and the catalyst has good activity and selectivity no matter the catalyst is terminal alkyne or internal alkyne.

4. In the partial hydrogenation reaction process, carbon dioxide and a small amount of alcohol amine are introduced into the reaction system, so that the occurrence of dimerization side reaction of raw material alkynol is reduced, and the selectivity of allyl alcohol products is effectively improved.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

The main raw material information is as follows:

methylbutynol, methylpentanynol, dehydrolinalool, dihydrodehydrolinalool, tetrahydrodehydronerolidol, 1, 4-butynediol, dehydroisophytol, aletin, purity >99%; dehydronerolidol, dehydroethyl linalool, outsourced, north dazheng, 99% purity.

Calcium carbonate, tetrachloropalladate, aldrich reagent; manganese acetate, molybdenum acetate, tungsten tetrachloride, alpha-epothilone reagent; sodium formate, lead acetate, cadmium acetate, manganese acetate, and acla Ding Shiji; deionized water, self-making. Diethanolamine, triethanolamine, triisopropanolamine, >99%, aladine.

Ethanol, industrially pure; tetrahydrofuran, isopropanol, AR, ala Ding Shiji.

The gas chromatography test conditions of the present invention are as follows:

moilent 7820B gas chromatography, HP-Innowax capillary column; solvent: dichloromethane (or no solvent); sample injection volume: 1 μl; sample inlet temperature: 240 ℃; split ratio: 30/1; hydrogen flow rate: 40mL/min; tail blow flow: 25mL/min; air flow rate: 400mL/min; column flow rate: 1.5mL/min; heating program: the initial column temperature is 35 ℃, and the column is kept for 5min; raising the temperature to 100 ℃ at a speed of 6 ℃/min; then the temperature is raised to 240 ℃ at a speed of 30 ℃/min, and the mixture is kept for 5min.

Example 1

Pd-Mn-Pb (II)/CaCO ₃ (I) partial hydrogenation catalyst.

10.0G of a calcium carbonate carrier was precisely weighed at room temperature, added to a flask, and then 100mL of deionized water was added to obtain a suspension, to which an aqueous solution of tetrachloropalladate (30 mg/mL,42.3 mL) and an aqueous solution of manganese acetate (25 mg/mL,2.0 mL) were slowly added with stirring. After the addition was completed, the mixture was stirred at room temperature for 1 hour, then heated to 80℃and 0.5M sodium formate solution (10.2 mL) was added over 30 minutes, the reaction mixture was stirred for 1 hour, and the catalyst powder was washed with deionized water by filtration and washed several times to remove inorganic salt impurities. The resulting powder was dried in an oven at 80℃for 12 hours. The dry powder obtained above was suspended in 40mL deionized water and stirred for 10 minutes. Adding an aqueous solution of lead acetate (5.0 wt percent, 12.6 g) into the mixture for 20 minutes, heating the mixture to 80 ℃ after the addition, keeping the temperature for 1 hour, cooling, filtering to obtain gray catalyst powder, and washing a catalyst filter cake for 2-3 times by adopting deionized water; the resulting catalyst was dried in a vacuum oven at 60℃under a pressure of 20mbar to give Pd-Mn-Pb (II)/CaCO ₃ catalyst (10.8 g). The theoretical loadings of palladium and manganese were 5% and 0.5%, respectively.

Example 2

Pd-Mo-Pb (II)/CaCO ₃ partial hydrogenation catalyst.

5.6G of calcium carbonate carrier was precisely weighed at room temperature, added to a flask, and then 50mL of deionized water was added to obtain a suspension, to which an aqueous solution of tetrachloropalladac acid (30 mg/mL,23.7 mL) and an aqueous solution of molybdenum acetate (18 mg/mL,3.3 mL) were slowly added with stirring. After the addition was completed, the mixture was stirred at room temperature for 1 hour, then heated to 80℃and 0.5M sodium formate solution (5.7 mL) was added over 30 minutes, the reaction mixture was stirred for 1 hour, and the catalyst powder was washed with deionized water by filtration and washed several times to remove inorganic salt impurities. The resulting powder was dried in an oven at 80℃for 12 hours. The dry powder obtained above was suspended in 40mL deionized water and stirred for 10 minutes. Adding an aqueous solution of lead acetate (5.0 wt percent, 7.0 g) into the mixture for 20 minutes, heating the mixture to 80 ℃ after the addition, keeping the temperature for 1 hour, cooling, filtering to obtain gray catalyst powder, and washing a catalyst filter cake for 2-3 times by adopting deionized water; the resulting catalyst was dried in a vacuum oven at 60℃under a pressure of 20mbar to give Pd-Mo-Pb (II)/CaCO ₃ catalyst (6.05 g). The theoretical loadings of palladium and molybdenum were 5% and 0.5%, respectively.

Example 3

Pd-W-Pb (II)/CaCO ₃ partial hydrogenation catalyst.

6.3G of calcium carbonate carrier was precisely weighed at room temperature, added to a flask, and then 50mL of deionized water was added to obtain a suspension, to which an aqueous solution of tetrachloropalladac acid (30 mg/mL,26.7 mL) and an aqueous solution of tungsten tetrachloride (21 mg/mL,2.9 mL) were slowly added with stirring. After the addition was completed, the mixture was stirred at room temperature for 1 hour, then heated to 80℃and 0.5M sodium formate solution (6.4 mL) was added over 30 minutes, the reaction mixture was stirred for 1 hour, and the catalyst powder was washed with deionized water by filtration and washed several times to remove inorganic salt impurities. The resulting powder was dried in an oven at 80℃for 12 hours. The dry powder obtained above was suspended in 40mL deionized water and stirred for 10 minutes. Adding an aqueous solution of lead acetate (5.0 wt percent, 8.0 g) into the mixture for 20 minutes, heating the mixture to 80 ℃ after the addition, keeping the temperature for 1 hour, cooling, filtering to obtain gray catalyst powder, and washing a catalyst filter cake for 2-3 times by adopting deionized water; the resulting catalyst was dried in a vacuum oven at 60℃under a pressure of 20mbar to give Pd-W-Pb (II)/CaCO ₃ catalyst (6.8 g). The theoretical loadings of palladium and cobalt were 5% and 0.5%, respectively.

Example 4

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of methylbutinol to obtain methylbutinol.

The autoclave of 1L stainless steel was sealed at room temperature, filled with nitrogen of 0.5MPa, and then left for at least 30 minutes, the nitrogen pressure in the autoclave did not drop, indicating that the autoclave was well sealed. The autoclave was purged with nitrogen to atmospheric pressure, and then charged with 2-methyl-3-butyn-2-ol (100.4 g,0.85 mol), ethanol (100 mL), triethanolamine (0.5 g), and Pd-Mn-Pb (II)/CaCO ₃ (1.0 g), the catalyst prepared in example 1, to obtain a gray suspension, most of which was precipitated at the bottom of the reaction solution. After the charging is finished, the autoclave is resealed, nitrogen is filled and discharged for 3 times, and 0.3MPa of each time is used for replacing the air in the autoclave; then closing a nitrogen pipeline valve, opening a hydrogen pipeline valve, filling and discharging hydrogen for 3 times, wherein each time is 0.3MPa, replacing nitrogen in the autoclave with hydrogen, and finally filling 0.1MPa carbon dioxide and 1.9MPa hydrogen into the autoclave, and keeping the pressure constant (2.0 MPa) in the reaction process. The autoclave was started to stir and the jacket was heated at a stirring speed of 600r/min in order to bring the catalyst and the substrate into sufficient contact. After the temperature in the kettle is raised to 40 ℃ (the temperature raising process is about 15-20 minutes), the constant temperature and the constant pressure are kept for 2 hours of reaction. Sampling is carried out at fixed time in the partial hydrogenation reaction process, a double valve and a bottom inserting pipe are adopted for sampling, a sintering head filter is arranged at the bottom of the bottom inserting pipe, a catalyst can be filtered, the reaction liquid obtained by sampling is colorless transparent liquid, the sampling amount is 0.5g each time, the reaction liquid is added into a certain amount of chromatographic pure acetonitrile, the content of 2-methyl-3-butyn-2-ol, 2-methyl-3-buten-2-ol and tertiary amyl alcohol in the reaction liquid is analyzed by GC, and the conversion rate and the selectivity are determined. After 3 hours, the conversion rate of the raw material 2-methyl-3-butyn-2-ol is more than 99.5 percent, the 2-methyl-3-buten-2-ol in the product is 98.9 percent, the tertiary amyl alcohol is 0.7 percent, and other byproduct impurities are 0.4 percent.

Examples 5 to 9

In order to compare the catalytic effect of the different catalysts prepared according to the invention, examples 5 to 10 are further provided, which differ from example 4 in that different catalysts are used, the other reaction conditions and operating steps being completely identical. The catalyst preparation described in examples 7-9 was identical to example 1 except that the amounts of palladium salt, manganese salt and poisoning agent salt added were varied. The conversion and selectivity of the catalyst for the partial hydrogenation of 2-methyl-3-butyn-2-ol for the different catalysts are shown in the following table. As can be seen from the data in the table, the catalysts Pd-Mn-Pb (II)/CaCO ₃ and Pd-Mo-Pb (II)/CaCO ₃ have the best catalyst effect.

TABLE 1

Numbering device	Catalyst	Pd-M-M loading/%	Conversion/%	Selectivity/%
					Example 5	Pd-Mn-Pb(II)/CaCO₃	1.0-0.1-0.1	97	95.1
Example 6	Pd-Mn-Pb(II)/CaCO₃	10.0-0.3-5.0	99	89.6
					Example 7	Pd-W-Zn(II)/CaCO₃	5.0-0.5-2.0	83	98.1
Example 8	Pd-Mo-Cr(II)/CaSO₄	5.0-0.6-2.0	99	91.1
					Example 9	Pd-Mo-Pb(II)/CaCO₃	5.0-1.0-1.0	99	95.4

Example 10

Pd-Mn-Pb (II)/CaCO ₃ catalyzes partial hydrogenation of methyl pentynol to obtain methyl pentynol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: methyl pentynyl alcohol (3-methyl-1-pentyn-3-ol) (98.14 g,1.0 mol), solvent isopropanol (100 mL), triethanolamine (0.1 g), catalyst Pd-Mn-Pb (II)/CaCO ₃ (1.0 g). The reaction temperature is 40 ℃, the pressure is 1.0MPa (hydrogen is 0.95MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 5 hours; the experimental procedure and flow were identical to example 4. And GC analysis of the reaction solution, wherein the conversion rate of the raw material methyl pentynol is more than 99.5%, the target product methyl pentenol in the product is 98.9%, the excessive hydrogenation byproduct 3-methyl-3-amyl alcohol is 0.7%, and other byproduct impurities are 0.4%.

Example 11

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of dehydrolinalool to obtain linalool.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: dehydrolinalool (3, 7-dimethyl-6-octen-1-yn-3-ol) (99.0 g,0.65 mol), solvent ethanol (100 mL), triisopropanolamine (0.05 g), catalyst Pd-Mn-Pb (II)/CaCO ₃ (1.0 g). The reaction temperature is 60 ℃, the pressure is 1.5MPa (hydrogen is 1.45MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 3 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material dehydrolinalool is more than 99.5%, target product linalool in the product is 99.1%, excessive hydrogenation byproduct is 0.5%, and other byproduct impurities are 0.4%.

Example 12

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of the dihydro-dehydrolinalool to obtain the dihydro-linalool.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: dihydro-dehydrolinalool (3, 7-dimethyl-1-octyn-3-ol) (100.3 g,0.65 mol), solvent ethanol (100 mL), triethanolamine (0.05 g), catalyst Pd-Mn-Pb (II)/CaCO ₃ (1.0 g). The reaction temperature is 60 ℃, the pressure is 1.5MPa (hydrogen is 1.45MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 3 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material dihydro-dehydrolinalool is more than 99.5%, target product dihydro-linalool (3, 7-dimethyl-1-octen-3-ol) in the product is 98.8%, excessive hydrogenation byproduct is 0.7%, and other byproduct impurities are 0.5%.

Example 13

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of dehydronerolidol to obtain nerolidol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: dehydronerolidol (3, 7, 11-trimethyl-6, 10-dodecene-1-yn-3-ol) (99.2 g,0.45 mol), triethanolamine (0.2 g), solvent tetrahydrofuran (100 mL), catalyst Pd-Mn-Pb (II)/CaCO ₃ (0.5 g). The reaction temperature is 60 ℃, the pressure is 2.0MPa (hydrogen is 1.95MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 6 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis of the reaction solution, wherein the conversion rate of raw material dehydronerolidol is more than 99.5%, the target product nerolidol (3, 7, 11-trimethyl-1, 6, 10-dodecanetriene-3-ol) in the product is 99.0%, the excessive hydrogenation byproduct of the dehydronerolidol is 0.6%, and other byproduct impurities are 0.4%.

Example 14

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of 1, 4-butynediol to obtain 1, 4-butenediol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: 1, 4-butynediol (103.3 g,1.2 mol), solvent ethanol (100 mL), triethanolamine (0.05 g), catalyst Pd-Mn-Pb (II)/CaCO ₃ (2.1 g). The reaction temperature is 80 ℃, the pressure is 2.0MPa (hydrogen is 1.95MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 6 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material 1, 4-butynediol is more than 99.5%, the target product 1, 4-butylene glycol in the product is 99.3%, the excessive hydrogenation byproduct 1, 4-butanediol is 0.6%, and other byproduct impurities are 0.1%.

Example 15

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of dehydroethyl linalool to obtain ethyl linalool.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: dehydroethyl linalool (3, 7-dimethyl-6-nonen-1-yn-3-ol) (99.8 g,0.6 mol), triethanolamine (0.05 g), solvent ethanol (100 mL), catalyst Pd-Mn-Pb (II)/CaCO ₃ (1.0 g). The reaction temperature is 80 ℃, the pressure is 1.5MPa (hydrogen is 1.45MPa, carbon dioxide is 0.05 MPa), the stirring speed is 600r/min, and the reaction time is 4 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material dehydroethyl linalool is more than 99.5%, the target product ethyl linalool in the product is 98.6%, the excessive hydrogenation byproduct of the dihydroethyl linalool is 0.8%, and other byproduct impurities are 0.6%.

Example 16

Pd-Mn-Pb (II)/CaCO ₃ catalyzes the partial hydrogenation of dehydroisophytol to obtain isophytol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: dehydroisophytol (3, 7,11, 15-trimethyl-1-hexadecan-3-ol) (103.1 g,0.35 mol) triethanolamine (0.05 g), solvent ethanol (100 mL), catalyst Pd-Mn-Pb (II)/CaCO ₃ (0.5 g). The reaction temperature is 80 ℃, the pressure is 2.0MPa (hydrogen is 1.9MPa, carbon dioxide is 0.1 MPa), the stirring speed is 600r/min, and the reaction time is 4 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material dehydroisophytol is more than 99.5%, the target product isophytol (3, 7,11, 15-trimethyl-1-hexadecen-3-ol) in the product is 99.4%, the overhydrogenation product dihydroisophytol is 0.4%, and other byproduct impurities are 0.2%.

Example 17

Pd-Mo-Pb (II) O ₂/CaCO₃ catalyzes the partial hydrogenation of 3,7, 11-trimethyl-6-dodecen-1-yn-3-ol to obtain 3,7, 11-trimethyl-1, 6-dodecen-3-ol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: 3,7, 11-trimethyl-6-dodecen-1-yn-3-ol (100.1 g,0.45 mol), solvent ethanol (50 mL), diethanolamine (0.3 g), catalyst Pd-Mo-Pb (II)/CaCO ₃ (0.5 g). The reaction temperature is 60 ℃, the hydrogen pressure is 1.5MPa (hydrogen is 1.46MPa, carbon dioxide is 0.04 MPa), the stirring speed is 600r/min, and the reaction time is 4 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of the raw material 3,7, 11-trimethyl-6-dodecen-1-yn-3-ol is more than 99.5%, the target product 3,7, 11-trimethyl-1, 6-dodecene-3-ol in the product is 99.0%, the excessive hydrogenation byproduct 3-methyl-3-amyl alcohol is 0.6%, and other byproduct impurities are 0.4%.

Comparative example 1

The prior art 0.5% Pd/Al ₂O₃/ZnO is adopted to catalyze the partial hydrogenation of the 2-methyl-3-butine-2-alcohol to obtain the 2-methyl-3-butene-2-alcohol.

Experiments were performed using a 2L stainless steel autoclave, with the reaction batch: 2-methyl-3-butyn-2-ol (80.0 g,0.68 mol), catalyst 0.5% Pd/Al ₂O₃/ZnO (0.8 g). The reaction temperature is 65 ℃, the pressure is 0.3MPa, the stirring speed is 600r/min, and the reaction time is 3 hours; the experimental procedure and flow were exactly the same as in example 4. GC analysis reaction liquid, the conversion rate of raw material 2-methyl-3-butyn-2-ol is more than 99.3%, target product linalool 94.9%, excessive hydrogenation byproduct 3.5% and other byproduct impurity 1.6%.

As can be seen from the comparison of the above examples and comparative examples, the invention adopts the simple substances of tungsten, manganese, molybdenum and the like which have strong adsorption effect on the carbon-carbon triple bond as catalyst metal auxiliary agents, enhances the selective adsorption of the catalyst on the carbon-carbon triple bond substrate, and further improves the selectivity of partial hydrogenation reaction. Meanwhile, the catalyst disclosed by the invention has good performance and wide substrate application range, and both terminal alkyne and internal alkyne show good activity and selectivity. In addition, in the partial hydrogenation reaction process, carbon dioxide and a small amount of alcohol amine are introduced into the reaction system, so that the occurrence of dimerization side reaction of alkynol serving as a raw material is reduced, and the selectivity of an allyl alcohol product is effectively improved.

Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims

1. A triple bond partial hydrogenation method for partially hydrogenating alkyne raw materials to obtain alkene, which is characterized in that the hydrogenation method adopts alcohol amine and palladium-containing catalyst to cooperate to obtain controlled hydrogenation reaction;

Wherein, the hydrogenation method is added with gaseous carbon dioxide,

Wherein the palladium-containing catalyst consists of the following components:

(I) 84.5 to 98.8 weight percent of carrier;

(II) 1-10wt% of main catalyst metal palladium;

(III) 0.1 to 0.5 weight percent of additive metal;

(IV) poisoning agent, 0.1-5.0wt%;

wherein the carrier is one or more of calcium carbonate, barium sulfate, aluminum oxide and silicon oxide;

Wherein the auxiliary metal is one or more of elemental tungsten, elemental molybdenum and elemental manganese;

Wherein the poisoning agent is one or more of lead salt, zinc salt and chromium salt;

the percentages being based on the total mass of the catalyst.

2. The partial hydrogenation process according to claim 1, wherein the alcohol amine is one or more of triethanolamine, diethanolamine, diisopropanolamine and triisopropanolamine, and the alcohol amine is used in an amount of 0.05 to 0.5wt% of the substrate mass.

3. The partial hydrogenation process according to claim 1, wherein the hydrogenation process is a batch reaction or a continuous reaction.

4. The partial hydrogenation method according to claim 3, wherein the reaction time of the batch reaction is 2 to 6 hours; the temperature of the reaction is 40-80 ℃; the pressure of the reaction gas is 0.2-2.0 MPa, the partial pressure of carbon dioxide is 1-5%, the rest is hydrogen, and the gas pressure is kept stable in the reaction process; the catalyst is used in an amount of 0.5 to 2.0wt% relative to the mass of the substrate.

5. The partial hydrogenation process according to claim 1, wherein the partial hydrogenation reaction may be carried out without or with the addition of a solvent; if a solvent is added, the solvent is one or more of methanol, ethanol, isopropanol, acetone and tetrahydrofuran.

6. The partial hydrogenation process according to claim 5, wherein the solvent added in the partial hydrogenation reaction is ethanol.

7. The partial hydrogenation process according to claim 1, wherein the catalyst preparation process comprises the steps of:

8. The partial hydrogenation process according to claim 7, wherein the palladium salt in SS1 is one or more of palladium chloride, palladium nitrate, palladium acetate and dihydrotetrapalladium acid;

and/or the auxiliary metal is one or more of molybdenum nitrate, molybdenum acetate, manganese nitrate and tungsten tetrachloride.

9. The partial hydrogenation process according to claim 7, wherein the poisoning agent in SS2 is one or more of lead acetate, zinc oxide, zinc acetate, zinc chloride, and cadmium acetate.

10. Use of a triple bond partial hydrogenation process according to any one of claims 1 to 9 for the partial hydrogenation of alkyne feedstock to produce alkene.

11. The use according to claim 10, wherein the alkyne raw material is any one of methylbutynol, methylpentanynol, dehydrolinalool, dihydrodehydrolinalool, dehydronerolidol, 1, 4-butynediol and dehydroisophytol.