CN114411179A - Method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation - Google Patents

Method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation Download PDF

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CN114411179A
CN114411179A CN202111671492.3A CN202111671492A CN114411179A CN 114411179 A CN114411179 A CN 114411179A CN 202111671492 A CN202111671492 A CN 202111671492A CN 114411179 A CN114411179 A CN 114411179A
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butanediol
butynediol
cathode
foam
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张健
杨三银
卜军
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Northwestern Polytechnical University
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Abstract

The invention relates to a method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation, which adopts a flow type or static type electrolytic cell, a self-supporting catalyst and a nanoparticle catalyst by a foam metal growth method, and uses a three-electrode or two-electrode system to carry out electrochemical performance test. The method is an electro-catalysis technology which is green, safe, low in cost and high in efficiency. Compared with the traditional thermal catalysis technology, the method can be used for reducing the reactant 1, 4-butynediol into 1, 4-butanediol by one-step hydrogenation at normal temperature and normal pressure, and solves the key problems of high temperature and high pressure, long flow path and the like of the traditional thermal catalysis hydrogenation process. Meanwhile, water is used as a hydrogen source to replace flammable and explosive hydrogen, so that energy consumption and potential danger can be greatly reduced, the development requirements of green chemical industry are met, and the method has great development prospect and strategic significance.

Description

Method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation
Technical Field
The invention belongs to a method for preparing 1, 4-butanediol, and relates to a method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation.
Background
1, 4-Butanediol (BDO) is a carbon-carbon triple bond saturated hydrogenation product of 1, 4-butynediol, is an organic synthesis intermediate with wide application and large market demand, and downstream products mainly comprise polyurethane, polyester and the like. Compared with the processes of ethylene glycol, propylene glycol and the like, the polyester product prepared by 1, 4-butanediol has more excellent comprehensive performance. Particularly, the PBT resin synthesized by 1, 4-butanediol and terephthalic acid has balanced physical properties and good hardness, rigidity, toughness and moldability, is an indispensable high-quality organic material for industries such as electronics, instruments, automobiles and the like, and gradually replaces metals and thermosetting plastics in certain industries. In recent years, with the strong promotion of the national policy of plastic (plastic) prohibition, BDO is used as an important raw material of degradable materials, and new development opportunities are met.
The BDO production process technology comprises an alkyne aldehyde method, an allyl alcohol method, a butadiene method, a dichlorobutene hydrolysis method and a maleic anhydride method. Due to the mature technology of the Reppe method and obvious economic benefit, most of BDO enterprises in China currently adopt the alkyne-aldehyde method, the effective capacity of BDO in China is 222.4 ten thousand tons in 2020, wherein the capacity of the alkyne-aldehyde method is 202.4 ten thousand tons accounting for 91 percent, and 588 ten thousand tons of newly increased capacity is planned to be dominant in the future.
Acetylene and formaldehyde are used as main raw materials in the alkynal method, 1, 4-Butynediol (BYD) is generated under the catalysis of copper/bismuth, impurities are filtered out, and hydrogenation is carried out to generate BDO. Wherein, the BYD hydrogenation process flow comprises two steps: 1) carrying out hydrogenation reaction on BYD in a slurry bed at the temperature of 60-70 ℃ and the pressure of 2-2.5 MPa to obtain a BDO crude liquid, wherein the crude liquid contains a large amount of water and a small amount of generated unsaturated carbonyls besides BDO; 2) and further hydrogenating the acetylene alcohol which is not completely hydrogenated in the first step in a fixed bed reactor at the temperature of 110-160 ℃ and the pressure of 12-21 MPa to generate a final product BDO. The second hydrogenation step is critical to the quality and yield of BDO and is central to the overall production process.
Because the Reppe two-step hydrogenation is a high-pressure hydrogenation reaction process, the reactor is required to have high mechanical strength and high pressure resistance; and the production flow is longer, the reaction conditions are harsh, the reaction temperature, the hydrogen partial pressure, the pH value and the like need to be strictly controlled in production to reduce the generation of byproducts, and the yield of BDO is ensured. Compared with the traditional thermocatalytic hydrogenation, the electrochemical catalytic hydrogenation does not need hydrogen to provide a hydrogen source, but generates active hydrogen in situ on the surface of a cathode catalyst by electrochemical reduction with water or electrolyte solution, and has lower reaction energy barrier and milder reaction conditions (room temperature and normal pressure). Meanwhile, the electric energy required by the electrochemical hydrogenation can be provided by renewable energy sources, and the method is a green and environment-friendly chemical synthesis method. Therefore, the electrocatalytic technology is used for replacing a thermocatalytic process to reduce 1, 4-butynediol into 1, 4-butanediol by hydrogenation, and the method is a novel technology with great development potential.
In view of the above, we develop an electrocatalytic technology for directly synthesizing 1, 4-butanediol from 1, 4-butynediol at normal temperature and normal pressure by one step, which not only solves a series of problems of harsh reaction conditions, long flow, difficult product separation, high cost and the like of the traditional thermocatalytic method, but also meets the requirements of green and double-carbon development of the current society, and becomes an ideal and efficient BDO synthesis technical route.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation, and extensive and intensive research is carried out on a device system and a catalyst of a reaction, so that the method is carried out safely and efficiently at room temperature and room pressure, and has high conversion rate and high selectivity.
Technical scheme
A method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation is characterized in that a flow type electrolytic cell or an H-type electrolytic cell is adopted, reactant 1, 4-butynediol is added into a cathode electrolyte, and a liquid-phase product 1, 4-butanediol is collected at a reaction output end.
When the flow type electrolytic cell is adopted, the steps are as follows:
step a 1: spraying catalyst A load on the ion exchange membrane to prepare a cathode, wherein the load after the catalyst is sprayed is 0.001-100 mg/cm2(ii) a Or spraying a catalyst A on the conductive substrate to prepare the working electrode, wherein the loading capacity of the sprayed catalyst is 0.001-100 mg/cm2(ii) a The conductive substrate includes, but is not limited to, metal foam, carbon paper or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam;
spraying a catalyst B on the anode;
step a2, electrocatalytic hydrogenation: adding reactant 1, 4-butynediol into the catholyte, performing electrochemical reduction reaction on the alkynol by adopting a three-electrode or two-electrode system, and collecting a liquid-phase product 1, 4-butanediol.
When the H-shaped electrolytic cell is adopted, the method comprises the following steps:
step b 1: the working electrode is prepared by spraying a catalyst A on a conductive substrate, and the loading capacity of the sprayed catalyst is 0.001-100 mg/cm2(ii) a The conductive substrate includes, but is not limited to, metal foam, carbon paper or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam;
spraying a catalyst B on the anode;
step b2, electrocatalytic hydrogenation: electrolyte is added into a cathode chamber and an anode chamber, reactant 1, 4-butynediol is added into a cathode chamber, an oxygen-producing catalytic material or a selective oxidation material is adopted for an electrode, and a liquid-phase product 1, 4-butanediol is collected.
When the cathode is a cathode sprayed with a catalyst on the foam metal, an ion exchange membrane is arranged between the cathode and the anode for isolation.
When the foam metal is used as the cathode, the preparation steps are that firstly, the foam nickel is washed by dilute hydrochloric acid, ionized water and absolute ethyl alcohol in sequence, and then dried in vacuum at 60 ℃. And then immersing the precursor solution prepared by nickel nitrate hexahydrate and hexamethylenetetramine HMT in the hydrothermal solution for 8 hours at the temperature of 90-100 ℃. Cooling, taking out, ultrasonically cleaning with ionized water, and finally transferring to a vacuum drying oven for vacuum drying at 80 ℃ for 10h and taking out; the other metal arrays can be prepared by adopting the method when growing on the foam metal.
The slurry of the catalyst A or the catalyst B is as follows: uniformly dispersing the catalyst powder into isopropanol or other solvents, adding a Nafion solution after full ultrasonic mixing, and oscillating for 10-120 min by using an ultrasonic bath to obtain the catalyst slurry.
The powder of the catalyst A includes but is not limited to particles based on Ni, Cu, Fe, Co, Pt, Pd, Au, Ag and the like, single metal and bimetallic catalysts thereof, metal phthalocyanine catalysts and metal carbene catalysts.
Powders of the catalyst B include, but are not limited to Ir, Ru-based catalysts and non-noble metal based catalysts based on Fe, Co, Ni.
The electrolyte of the electrolyte in the cathode electrolyte and the electrolyte in the anode are acidic, neutral and alkaline electrolytes or solid electrolytes.
The electrolyte of the cathode electrolyte and the electrolyte in the anode comprises but is not limited to 0.01-10M KHCO3Aqueous solution, 0.01-5M hydrochloric acid aqueous solution, 0.01-5M sulfuric acid aqueous solution, 0.01-5M KCl aqueous solution or 0.01-10M KOH aqueous solution, propylene carbonate PC/tetrabutylammonium perchlorate TBAP organic solution, PC and ethylene glycol dimethyl ether DME organic solvent, 1-butyl 3-methylimidazole trifluoromethylsulfonate [ Bmim ]][CF3SO3]Propylene carbonate PC solution.
Advantageous effects
The invention provides a method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation, which adopts a flow type or static type electrolytic cell, a self-supporting catalyst and a nanoparticle catalyst by a foam metal growth method, and uses a three-electrode or two-electrode system to carry out electrochemical performance test. The method is an electro-catalysis technology which is green, safe, low in cost and high in efficiency. Compared with the traditional thermal catalysis technology, the method can be used for reducing the reactant 1, 4-butynediol into 1, 4-butanediol by one-step hydrogenation at normal temperature and normal pressure, and solves the key problems of high temperature and high pressure, long flow path and the like of the traditional thermal catalysis hydrogenation process. Meanwhile, water is used as a hydrogen source to replace flammable and explosive hydrogen, so that energy consumption and potential danger can be greatly reduced, the development requirements of green chemical industry are met, and the method has great development prospect and strategic significance.
The invention has the innovativeness that:
(1) in the method, the reaction is carried out at normal temperature and normal pressure, so that the safety performance is improved, and the energy consumption and the manufacturing cost of the high-temperature high-pressure reactor are reduced;
(2) in the method, 1, 4-butynediol can be reduced into 1, 4-butanediol by one step of hydrogenation reaction, so that the reaction flow is shortened, and the occurrence of side reactions is reduced;
(3) in the method, non-noble metal catalysts such as nickel, copper and the like are adopted, so that the cost is reduced;
(4) in the method, water is used as a hydrogen source, explosive hydrogen is avoided being used as the hydrogen source, and the development requirement of green chemical industry is met.
Drawings
FIG. 1 is a schematic view of a flow-type electrolytic cell
FIG. 2 is a schematic diagram of the structure of a proton exchange membrane electrolytic cell
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
in order to achieve the above object, the hydrogenation of 1, 4-butynediol is carried out using a flow-type or static-type electrolytic cell. The catalysts are classified into foam metal growth self-supporting catalysts and nanoparticle catalysts according to the difference of the catalysts.
The hydrogenation reaction of 1, 4-butynediol is carried out by adopting a flowing or static electrolytic cell.
First, a cathode catalyst was prepared: the preparation method is a membrane electrode method or a foam metal (foam nickel and the like) growth method. Hg/HgO or Ag/AgCl (full cell test has no reference electrode) is used as the reference electrode of the electrolytic cell, and the anode and the cathode are isolated by an ion exchange membrane.
The preparation steps of the cathode catalyst of the membrane electrode method are as follows: first, a slurry of the catalyst is prepared: uniformly dispersing 10 mg-10 g of catalyst powder into 2 mL-2L of isopropanol solvent, fully ultrasonically mixing, adding 30 mu L-30 mL of electrolyte solution, and oscillating for 10-120 min by using an ultrasonic bath to uniformly disperse the catalyst powder to obtain catalyst slurry. Then, the proton exchange membrane and the conductive substrate are cut according to the size of the area to be activated. Transferring the mixed slurry into a spray pen kettle externally connected with high-pressure gas, adjusting the gas pressure to be more than 0.2Mpa, and adjusting the liquid outlet speed and the gas outlet speed to ensure that the sprayed catalyst slurry spray can be rapidly evaporated at a given operating temperature. And uniformly spraying the slurry on an ion exchange membrane or a conductive substrate, and then putting the coated substrate into an oven to be dried for 30min at the temperature of 80 ℃.
The proton exchange membrane or the conductive substrate is arranged on a flat heating table, and the heating temperature is 50-100 ℃, preferably 70-90 ℃. The conductive substrate includes, but is not limited to, carbon fiber paper, carbon fiber woven fabric, non-woven fabric, carbon black, biomass carbon cloth, metal, non-metal substrate, carbon-based material substrate such as graphene and carbon nanotube, and the like.
The preparation steps of the cathode catalyst of the growth method are as follows: and cleaning the foamed nickel with dilute hydrochloric acid, ionic water and absolute ethyl alcohol in sequence, and drying at 60 ℃ in vacuum. Then immersing the precursor solution prepared by nickel nitrate hexahydrate and Hexamethylenetetramine (HMT) in the hydrothermal solution for 8 hours at the temperature of 80-110 ℃ and under the temperature of 90-100 ℃. Cooling, taking out, ultrasonically cleaning with ionized water, and finally transferring to a vacuum drying oven for vacuum drying at 80 ℃ for 10h to take out. Other metal arrays grown on foam metal can be prepared by similar methods.
Secondly, adding a reactant 1, 4-butynediol into the catholyte, performing electrochemical performance test by adopting a three-electrode or two-electrode system, and finally collecting a liquid-phase product and analyzing by using a chromatographic method. Compared with the traditional thermal catalysis technology, the method can directly catalyze and reduce the butynediol reactant into the 1, 4-butanediol at normal temperature and normal pressure without consuming hydrogen, can greatly reduce the energy consumption and potential danger in the process by taking water as a hydrogen source, better meets the requirements of green chemical industry, and has great strategic significance. The key point is cathode reaction, 1,4 butynediol reactant adsorbed on a cathode catalyst and active hydrogen obtained by electrolyzing water are subjected to reduction reaction, and triple bonds are hydrogenated and reduced into single bonds, so that 1,4 butanediol is finally formed and desorbed from the surface of the catalyst.
The electrolyte of the catholyte and the anolyte is acidic, neutral or alkaline electrolyte or solid electrolyte (including but not limited to 0.01-10M KOH aqueous solution and 0.01-10M KHCO)3An aqueous solution, 0.01 to 5M hydrochloric acid aqueous solution, 0.01 to 5M sulfuric acid aqueous solution, 0.01 to 5M KCl aqueous solution, 0.01 to 10M KOH aqueous solution, Propylene Carbonate (PC)/tetrabutylammonium perchlorate (TBAP) organic solution, PC and ethylene glycol dimethyl ether (DME) organic solvent, 1-butyl 3-methylimidazole trifluoromethanesulfonic acid salt ([ Bmim)][CF3SO3]) Propylene Carbonate (PC) solution, etc.).
The catalyst of the working electrode includes but is not limited to particles of Ni, Cu, Fe, Co, Pt, Pd, Au, Ag and the like, single metal and bimetallic catalysts thereof, metal phthalocyanine catalysts, metal carbene catalysts and the like; the counter electrode catalyst is Ir, Ru-based catalyst and non-noble metal-based catalyst based on Fe, Co, Ni and the like.
The invention is further illustrated by the following detailed description of the invention, which raw materials are commercially available from the open literature unless otherwise specified.
The electrocatalytic hydrogenation reduction reaction of 1, 4-butynediol to 1, 4-butanediol comprises the following steps:
[ example 1 ]
(1) Preparing a foamed nickel catalyst: a. performing ultrasonic treatment on the foamed nickel for 15min by using 1M dilute hydrochloric acid, cleaning by using deionized water and absolute ethyl alcohol, and performing vacuum drying at 60 ℃; b. soaking foamed nickel into a deionized water solution containing nickel nitrate hexahydrate and Hexamethylenetetramine (HMT), and placing the soaked foamed nickel into an air-blowing drying oven to be hydrothermal for 8 hours at the temperature of 95 ℃; c. and naturally cooling, taking out the foamed nickel sample, putting the foamed nickel sample into deionized water, performing ultrasonic treatment for 5min, transferring the sample into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 10h, and taking out the sample.
(2) Foamed nickel is used as the cathode of the electrolytic cell, a cobalt sheet is used as the anode of the electrolytic cell, the catholyte and the anolyte both adopt 1M KOH solution, and the anion chamber and the cation chamber are separated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst foam nickel, and when the reaction product alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 2 ]
(1) Preparing Ni nanoparticle catalyst slurry: 25mg of Ni nanoparticle catalyst powder was dispersed in 15mL of isopropanol, then 75. mu.L of Nafion solution (5 wt%) was added, stirred and ultrasonically dispersed for 90 min.
(2) Uniformly spraying Ni nanoparticle slurry on a carbon fiber paper conductive substrate to serve as an electrolytic cell cathode, taking Hg/HgO as an electrolytic cell reference electrode, taking a cobalt sheet as an electrolytic cell anode, wherein electrolyte of the cathode and the anode is 1M KOH solution, and the cathode and the anode are isolated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a static electrolytic cell of a three-electrode system, and carrying out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst Ni nanoparticles, and when the reaction product alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 3 ]
(1) Preparing Ni nanoparticle catalyst slurry: 25mg of Ni nanoparticle catalyst powder was dispersed in 15mL of isopropanol, followed by addition of 75 μ L of an solution (5 wt%), stirring and sonication for 90 min.
(2) The Ni nano-particle slurry is uniformly sprayed on the surface of a proton exchange membrane by adopting a precise spraying device to be used as an electrolytic cell cathode, a cobalt sheet is used as an electrolytic cell anode, both a catholyte and an anolyte are 1M KOH solution, and a cathode chamber and an anode chamber are isolated by an exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst Ni nanoparticle membrane electrode, and when the reaction product alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 4 ]
(1) Preparing a foamed copper-based catalyst: a. cleaning the foam copper, respectively ultrasonically cleaning the foam copper by using 1M hydrochloric acid, acetone and ethanol for 5-10min, and drying the foam copper by using nitrogen; b. preparing sodium hydroxide and ammonium persulfate solution with a certain concentration, and immersing the dried foamy copper in the solution for 20-50min to uniformly grow copper hydroxide; c. reducing the copper into copper in a tubular furnace at the temperature of 100 ℃ and 300 ℃ to obtain the foamed copper-based catalyst.
(2) The foamed copper-based catalyst is used as the cathode of an electrolytic cell, a cobalt sheet is used as the anode of the electrolytic cell, the catholyte and the anolyte are both 1M KOH solution, and a cathode chamber and an anode chamber are separated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst copper foam base growth copper, and when a reactant alkynol reacts for 1 hour, a liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 5 ]
(1) Preparing Pd/graphite nano-particle catalyst slurry: 25mg of Pd/graphite nanoparticle catalyst powder was dispersed in 15mL of isopropanol, then 75. mu.L of Nafion solution (5 wt%) was added, stirred and ultrasonically dispersed for 90 min.
(2) Uniformly spraying the Pd/graphite nano-particle slurry on the surface of a proton exchange membrane by adopting a precise spraying device to be used as an electrolytic cell cathode, and using a cobalt sheet electrode as an electrolytic cell anode; both the catholyte and anolyte were 0.5M H2SO4The solution and the yin and yang chambers are separated by a proton exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The catalyst Pd/graphite nano-particles are characterized by the catalytic activity by a potentiostatic method, and when a reactant alkynol reacts for 1 hour, a liquid-phase product 1, 4-butanediol is analyzed by chromatography.
[ example 6 ]
(1) Preparing carbene nickel catalyst slurry: 25mg of the nickel carbene catalyst was dispersed in 15mL of isopropanol, and then 75. mu.L of Nafion solution (5 wt%) was added, stirred and ultrasonically dispersed for 90 min.
(2) Uniformly spraying the carbene nickel slurry on a carbon fiber paper conductive substrate to be used as an electrolytic cell cathode, and using a cobalt sheet as an electrolytic cell anode; the catholyte and the anolyte are both 1M KOH solution, and the anion chamber and the cation chamber are separated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(3) And (3) adopting a three-electrode system static electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst carbene nickel, and when the reaction product alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 7 ]
(1) Preparing catalyst slurry: 25mg of the nickel phthalocyanine catalyst was dispersed in 15mL of isopropanol, and then 75. mu.L of Nafion solution (5 wt%) was added, stirred and ultrasonically dispersed for 90 min.
(2) The method comprises the steps of uniformly spraying nickel phthalocyanine catalyst slurry on a carbon fiber paper conductive substrate to serve as an electrolytic cell cathode, using a cobalt sheet as an electrolytic cell anode, and isolating a catholyte and an anolyte which are both 1M PC and ethylene glycol dimethyl ether (DME) organic solvents by using an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(4) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst nickel phthalocyanine, and when the reactant alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 8 ]
(1) Preparing Pt nano-particle catalyst slurry: 25mg of Pt nanoparticles were dispersed in 15mL of isopropanol, then 75. mu.L of Nafion solution (5 wt%) was added, stirred and ultrasonically dispersed for 90 min.
(2) Uniformly spraying Pt nano-particle slurry on a proton exchange membrane to serve as an electrolytic cell cathode, and taking Ir/C as an electrolytic cell anode; both the catholyte and anolyte were 0.5M H2SO4The solution and the yin and yang chambers are separated by a proton exchange membrane. The reactant 1, 4-butynediol is introduced at the cathode.
(3) And (3) adopting a flow type electrolytic cell of a two-electrode system, and carrying out electrochemical performance test through an electrochemical workstation. The catalyst activity of the Pt nano particles is characterized by a potentiostatic method, and when a reactant alkynol reacts for 1 hour, a liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 9 ]
(1) The electrodeposition foam nickel catalyst is used as the cathode of an electrolytic cell, a cobalt sheet is used as the anode of the electrolytic cell, the catholyte and the anolyte are both 1M KOH solution, and a cathode chamber and an anode chamber are separated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(2) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The potentiostatic method characterizes the catalytic activity of the catalyst for electrodepositing foamed nickel, and when the reaction product alkynol reacts for 1 hour, the liquid-phase product 1, 4-butanediol is analyzed through chromatography.
[ example 10 ]
(1) Preparing a Ni-based alloy catalyst: the active components prepared by adopting a sol-gel method are metallic nickel, metallic copper and metallic zinc.
(2) The Ni alloy catalyst is used as the cathode of the electrolytic cell, the cobalt sheet is used as the anode of the electrolytic cell, and both the catholyte and the anolyte are 1M KHCO3The solutions are separated by an anion exchange membrane. 5mL of the reactant 1, 4-butynediol was added to the catholyte.
(4) And (3) adopting a three-electrode system flow type electrolytic cell to carry out electrochemical performance test through an electrochemical workstation. The catalytic activity of the Ni-based alloy catalyst is characterized by a potentiostatic method, and when a reactant alkynol reacts for 1 hour, a liquid-phase product 1, 4-butanediol is analyzed by chromatography.
In conclusion, the method uses water as a hydrogen source to replace flammable and explosive hydrogen, realizes one-step synthesis of 1, 4-butanediol by electrocatalytic hydrogenation of 1, 4-butynediol at room temperature and normal pressure, and solves the key problems of hydrogen use, high temperature, high pressure, long process flow and the like in the two-step hydrogenation by thermocatalysis.
In summary, the above embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention. Modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention as defined by the following claims.
TABLE 1 results of specific evaluation of catalysts
Figure BDA0003453128780000121

Claims (10)

1. A method for preparing 1, 4-butanediol by electrocatalysis of 1, 4-butynediol hydrogenation is characterized in that a flow type electrolytic cell or an H-type electrolytic cell is adopted, reactant 1, 4-butynediol is added into a cathode electrolyte, and a liquid-phase product 1, 4-butanediol is collected at a reaction output end.
2. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 1, wherein: when the flow type electrolytic cell is adopted, the steps are as follows:
step a 1: spraying catalyst A load on the ion exchange membrane to prepare a cathode, wherein the load after the catalyst is sprayed is 0.001-100 mg/cm2(ii) a Or spraying a catalyst A on the conductive substrate to prepare the working electrode, wherein the loading capacity of the sprayed catalyst is 0.001-100 mg/cm2(ii) a The conductive substrate includes, but is not limited to, metal foam, carbon paper or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam;
spraying a catalyst B on the anode;
step a2, electrocatalytic hydrogenation: adding reactant 1, 4-butynediol into the catholyte, performing electrochemical reduction reaction on the alkynol by adopting a three-electrode or two-electrode system, and collecting a liquid-phase product 1, 4-butanediol.
3. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 1, wherein: when the H-shaped electrolytic cell is adopted, the method comprises the following steps:
step b 1: spraying catalyst A on conductive substrate to obtain working electrodeThe loading capacity of the spraying agent after spraying is 0.001-100 mg/cm2(ii) a The conductive substrate includes, but is not limited to, metal foam, carbon paper or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam;
spraying a catalyst B on the anode;
step b2, electrocatalytic hydrogenation: electrolyte is added into a cathode chamber and an anode chamber, reactant 1, 4-butynediol is added into a cathode chamber, an oxygen-producing catalytic material or a selective oxidation material is adopted for an electrode, and a liquid-phase product 1, 4-butanediol is collected.
4. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 2, wherein: when the cathode is a cathode sprayed with a catalyst on the foam metal, an ion exchange membrane is arranged between the cathode and the anode for isolation.
5. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 2 or 3, wherein: when the foam metal is used as the cathode, the preparation steps are that firstly, the foam nickel is washed by dilute hydrochloric acid, ionized water and absolute ethyl alcohol in sequence, and then dried in vacuum at 60 ℃. And then immersing the precursor solution prepared by nickel nitrate hexahydrate and hexamethylenetetramine HMT in the hydrothermal solution for 8 hours at the temperature of 90-100 ℃. Cooling, taking out, ultrasonically cleaning with ionized water, and finally transferring to a vacuum drying oven for vacuum drying at 80 ℃ for 10h and taking out; the other metal arrays can be prepared by adopting the method when growing on the foam metal.
6. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 2 or 3, wherein: the slurry of the catalyst A or the catalyst B is as follows: uniformly dispersing the catalyst powder into isopropanol or other solvents, adding a Nafion solution after full ultrasonic mixing, and oscillating for 10-120 min by using an ultrasonic bath to obtain the catalyst slurry.
7. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 6, wherein: the powder of the catalyst A includes but is not limited to particles based on Ni, Cu, Fe, Co, Pt, Pd, Au, Ag and the like, single metal and bimetallic catalysts thereof, metal phthalocyanine catalysts and metal carbene catalysts.
8. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 6, wherein: powders of the catalyst B include, but are not limited to Ir, Ru-based catalysts and non-noble metal based catalysts based on Fe, Co, Ni.
9. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 2 or 3, wherein: the electrolyte of the electrolyte in the cathode electrolyte and the electrolyte in the anode are acidic, neutral and alkaline electrolytes or solid electrolytes.
10. The electrocatalytic hydrogenation of 1, 4-butynediol to 1, 4-butanediol as set forth in claim 10, wherein: the electrolyte of the cathode electrolyte and the electrolyte in the anode comprises but is not limited to 0.01-10M KHCO3Aqueous solution, 0.01-5M hydrochloric acid aqueous solution, 0.01-5M sulfuric acid aqueous solution, 0.01-5M KCl aqueous solution or 0.01-10M KOH aqueous solution, propylene carbonate PC/tetrabutylammonium perchlorate TBAP organic solution, PC and ethylene glycol dimethyl ether DME organic solvent, 1-butyl 3-methylimidazole trifluoromethylsulfonate [ Bmim ]][CF3SO3]Propylene carbonate PC solution.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115364856A (en) * 2022-09-20 2022-11-22 西北工业大学 Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof
CN116510748A (en) * 2023-07-04 2023-08-01 潍坊学院 Catalyst for preparing formic acid by photocatalytic reduction of carbon dioxide as well as preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR494652A (en) * 1917-04-03 1919-09-16 Paul Victor Henri Pascal Process for the synthetic manufacture of ethyl alcohol, its ethers, and other alcohols, glycols and hydrocarbons, from acetylene
US4864066A (en) * 1987-05-23 1989-09-05 Basf Aktiengesellschaft Preparation of alkanediols from alkynols
US5919349A (en) * 1996-05-23 1999-07-06 Basf Aktiengesellschaft Electrochemical reduction of organic compounds
CN1545160A (en) * 2003-11-27 2004-11-10 上海交通大学 Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated alcohol
WO2012095709A1 (en) * 2011-01-12 2012-07-19 Basf Se Process for the hydrogenation of 1,4-butynediol to tetrahydrofuran in the gas phase
CN105033241A (en) * 2015-06-04 2015-11-11 北京化工大学 Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials
US20190276941A1 (en) * 2016-09-22 2019-09-12 Siemens Aktiengesellschaft Selective Electrochemical Hydrogenation of Alkynes to Alkenes
CN110512228A (en) * 2019-09-16 2019-11-29 燕山大学 A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material
CN113388853A (en) * 2021-05-27 2021-09-14 杭州师范大学 Electrochemical catalysis method for highly selective hydrogenation of carbon-carbon triple bonds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR494652A (en) * 1917-04-03 1919-09-16 Paul Victor Henri Pascal Process for the synthetic manufacture of ethyl alcohol, its ethers, and other alcohols, glycols and hydrocarbons, from acetylene
US4864066A (en) * 1987-05-23 1989-09-05 Basf Aktiengesellschaft Preparation of alkanediols from alkynols
US5919349A (en) * 1996-05-23 1999-07-06 Basf Aktiengesellschaft Electrochemical reduction of organic compounds
CN1545160A (en) * 2003-11-27 2004-11-10 上海交通大学 Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated alcohol
WO2012095709A1 (en) * 2011-01-12 2012-07-19 Basf Se Process for the hydrogenation of 1,4-butynediol to tetrahydrofuran in the gas phase
CN105033241A (en) * 2015-06-04 2015-11-11 北京化工大学 Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials
US20190276941A1 (en) * 2016-09-22 2019-09-12 Siemens Aktiengesellschaft Selective Electrochemical Hydrogenation of Alkynes to Alkenes
CN110512228A (en) * 2019-09-16 2019-11-29 燕山大学 A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material
CN113388853A (en) * 2021-05-27 2021-09-14 杭州师范大学 Electrochemical catalysis method for highly selective hydrogenation of carbon-carbon triple bonds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115364856A (en) * 2022-09-20 2022-11-22 西北工业大学 Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof
CN115364856B (en) * 2022-09-20 2023-11-07 西北工业大学 Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof
CN116510748A (en) * 2023-07-04 2023-08-01 潍坊学院 Catalyst for preparing formic acid by photocatalytic reduction of carbon dioxide as well as preparation method and application thereof
CN116510748B (en) * 2023-07-04 2023-09-01 潍坊学院 Catalyst for preparing formic acid by photocatalytic reduction of carbon dioxide as well as preparation method and application thereof

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