Method for preparing high-carbon ester compound by combining electro-catalysis and thermocatalysis of crude acetylene and two-step cascade device

Abstract

The invention provides a method for preparing a high-carbon ester compound by combining electrocatalysis and thermocatalysis of crude acetylene and a two-step cascade device, firstly, an electrochemical reaction is carried out, under the action of an anode electrode, H < + > in an anolyte in an anode chamber enters a cathode chamber through a cation exchange membrane, under the action of a cathode electrode, H < + > in the anolyte enters the cathode chamber through a cation exchange membrane, and the high-carbon ester compound is prepared. Generating CO2 from HCO3 <-> and H < + > in the catholyte, and carrying out electroreduction reaction to obtain a gas-liquid mixture; and finally, introducing crude acetylene gas into the gas-liquid mixture, absorbing CO2 to obtain mixed gas containing C2H2 and CO, and then introducing the mixed gas into an acetylene carbonylation solution for acetylene carbonylation reaction to obtain the high-carbon ester compound. According to the electro-catalysis and thermocatalysis combined preparation method and the two-step cascade system designed by the invention, the crude acetylene is converted into a high-carbon ester product. The cascade process not only contributes to reduction of carbon emission, but also contributes to upgrading of low-value acetylene, and the commercial value and environmental value of acetylene industry are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of preparing high-carbon ester compounds from crude acetylene, and relates to a method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, and a two-step cascade device thereof. Background Art

[0002] Acetylene is the simplest unsaturated hydrocarbon and one of the important chemical raw materials. It can be obtained from natural gas or coal. Acetylene is a key gaseous raw material for the production of various organic chemicals and polymers, such as acetaldehyde, benzene, synthetic rubber, polyester plastics, etc. Acetylene is mainly produced by coal-based calcium carbide method or natural gas partial combustion cracking method. However, these processes inevitably produce a large amount of carbon dioxide (CO2) as a by-product, resulting in increased carbon emissions, exacerbating the greenhouse effect, and complicating the direct downstream utilization of acetylene, and making further upgrading of acetylene difficult.

[0003] Due to the thermodynamic stability of the CO2 molecule, direct CC coupling between acetylene and CO2 is very difficult. Therefore, the traditional acetylene upgrading process currently used is to convert CO2 into CO through the reverse water gas shift (RWGS) reaction, and then use highly reactive CO to carbonylate with C2H2 to produce high-carbon ester products, such as dimethyl maleate. However, this process faces the problems of high energy consumption and cost. First, the RWGS process requires high-purity CO2 as a raw material, and separating CO2 from acetylene will further increase energy consumption and operating costs. In addition, the RWGS process requires additional hydrogen and is carried out under harsh conditions of high temperature and pressure, resulting in high energy consumption and high cost.

[0004] Therefore, how to find a more suitable, low-energy, economical and efficient green device for producing high-carbon ester compounds from crude acetylene, and directly convert crude acetylene into high-value products, has become one of the focuses of attention of many forward-looking researchers in the industry. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a two-step cascade device and method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis. The two-step cascade device provided by the present invention can solve the problem of difficulty in utilizing low-value crude acetylene gas and CO2 emission reduction in the acetylene production process.

[0006] The present invention provides a two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, comprising:

[0007] Electrolytic cell;

[0008] A cation exchange membrane disposed in the electrolytic cell;

[0009] The cation exchange membrane is provided with an anode electrode on one side and a cathode electrode on the other side;

[0010] The cation exchange membrane separates the electrolytic cell into a cathode chamber and an anode chamber;

[0011] The anode chamber is provided with an anode chamber liquid inlet and an anode chamber liquid outlet;

[0012] an anode liquid storage device;

[0013] The anode liquid storage device is connected to the anode chamber liquid inlet and the anode chamber liquid outlet respectively;

[0014] The cathode chamber is provided with a cathode chamber liquid inlet and a cathode chamber liquid outlet;

[0015] cathode liquid storage device;

[0016] The cathode liquid storage device is connected to the cathode chamber liquid inlet and the cathode chamber liquid outlet respectively;

[0017] The cathode liquid storage device is connected to a crude acetylene source;

[0018] Acetylene carbonylation reaction unit;

[0019] The acetylene carbonylation reaction device is connected to the cathode liquid storage device.

[0020] Preferably, the anode liquid storage device is provided with a gas outlet;

[0021] The anode liquid storage device is provided with an anode liquid storage device liquid inlet pipeline connected to the anode chamber liquid outlet;

[0022] The outlet of the liquid inlet pipeline of the anode liquid storage device is located above the liquid level of the anode liquid storage device;

[0023] The anode liquid storage device is provided with an anode liquid storage device liquid outlet pipeline connected to the anode chamber liquid inlet;

[0024] The inlet of the liquid outlet pipeline of the anode liquid storage device is located below the liquid level of the anode liquid storage device;

[0025] The liquid outlet pipeline of the anode liquid storage device is provided with a first conveying device.

[0026] Preferably, the cathode liquid storage device is provided with a cathode liquid storage device liquid inlet pipeline connected to the cathode chamber liquid outlet;

[0027] The outlet of the liquid inlet pipeline of the cathode liquid storage device is located above the liquid level of the cathode liquid storage device;

[0028] The cathode liquid storage device is provided with a cathode liquid storage device liquid outlet pipeline connected to the cathode chamber liquid inlet;

[0029] The inlet of the liquid outlet pipeline of the cathode liquid storage device is located below the liquid level of the cathode liquid storage device;

[0030] A second conveying device is arranged on the liquid outlet pipeline of the cathode liquid storage device.

[0031] Preferably, a crude acetylene intake pipeline is provided on the cathode liquid storage device;

[0032] The inlet of the crude acetylene inlet pipeline is connected to a crude acetylene source;

[0033] The outlet of the crude acetylene inlet pipeline is located below the liquid level of the cathode liquid storage device;

[0034] The two-step cascade device also includes an electrochemical workstation;

[0035] The electrochemical workstation is connected to the anode electrode and the cathode electrode respectively.

[0036] Preferably, the cathode liquid storage device is provided with a mixed gas outlet;

[0037] The mixed gas outlet is located above the liquid level of the cathode liquid storage device;

[0038] The mixed gas outlet is connected to the gas inlet of the acetylene carbonylation reaction device;

[0039] The acetylene carbonylation reaction device is provided with a gas outlet.

[0040] Preferably, the material of the anode electrode includes a metal porous material or a metal porous material loaded with iridium oxide;

[0041] The material of the cathode electrode includes catalyst-loaded carbon cloth or catalyst-loaded carbon felt;

[0042] The catalyst includes one or more of nickel, iron, zinc, silver and porous noble metals;

[0043] The electrolyte in the cathode chamber is a bicarbonate solution;

[0044] The electrolyte in the anode chamber is a sulfuric acid solution;

[0045] The acetylene carbonylation reaction device is provided with an acetylene carbonylation solution.

[0046] The present invention also provides a method for preparing high carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, comprising the following steps:

[0047] 1) Under the condition of power supply, the electrochemical reaction is carried out. Under the action of the anode electrode, the water in the anode electrolyte in the anode chamber is decomposed into H +and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, the HCO3 in the cathode electrolyte in the cathode chamber - With H + Generate CO2, and then conduct CO2 electroreduction reaction to obtain CO, H2, OH - and a gas-liquid mixture of a catholyte;

[0048] 2) The crude acetylene gas is introduced into the gas-liquid mixture obtained in the above step, and the CO2 in the crude acetylene gas is absorbed to obtain a mixed gas containing C2H2 and CO. The mixed gas is then introduced into an acetylene carbonylation solution, and C2H2 and CO are catalyzed to undergo acetylene carbonylation reaction to obtain high carbon ester compounds.

[0049] Preferably, the anolyte is a dilute sulfuric acid solution;

[0050] The cathode electrolyte is a saturated bicarbonate solution;

[0051] The volume ratio of C2H2 and CO2 in the crude acetylene gas is (20-1): (1-20);

[0052] After the gas-liquid mixture absorbs CO2 in the crude acetylene gas, it returns to the cathode chamber to carry out the reaction in step 1).

[0053] Preferably, the high carbon ester compound is an ester compound having carbon atoms greater than or equal to 6;

[0054] The ester compound having carbon atoms greater than or equal to 6 includes one or more of dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate and dipentyl butenedioate;

[0055] The acetylene carbonylation solution comprises acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt and anhydrous lithium salt;

[0056] The alcohol solvent includes one or more of methanol, ethanol, propanol, butanol and pentanol;

[0057] The palladium salt includes one or more of palladium chloride, palladium bromide and palladium acetate.

[0058] Preferably, the anhydrous lithium salt includes one or more of anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide and anhydrous lithium iodide;

[0059] The volume ratio of acetonitrile to alcohol solvent is (5-100): (1-10);

[0060] The volume ratio of acetonitrile to methanesulfonic acid is (5-100): (0.05-1);

[0061] The mass volume ratio of the palladium salt and acetonitrile is (1-10) mg: (0.5-10) mL;

[0062] The mass ratio of the palladium salt to the anhydrous lithium salt is (1-10): (1-10).

[0063] The invention provides a two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, comprising: an electrolytic cell; a cation exchange membrane arranged in the electrolytic cell; an anode electrode is arranged on one side of the cation exchange membrane, and a cathode electrode is arranged on the other side; the cation exchange membrane separates the electrolytic cell into a cathode chamber and an anode chamber; the anode chamber is provided with an anode chamber liquid inlet and an anode chamber liquid outlet; an anode liquid storage device; the anode liquid storage device is respectively connected to the anode chamber liquid inlet and the anode chamber liquid outlet; the cathode chamber is provided with a cathode chamber liquid inlet and a cathode chamber liquid outlet; a cathode liquid storage device; the cathode liquid storage device is respectively connected to the cathode chamber liquid inlet and the cathode chamber liquid outlet; the cathode liquid storage device is connected to a crude acetylene source; an acetylene carbonylation reaction device; the acetylene carbonylation reaction device is connected to the cathode liquid storage device. Compared with the prior art, the present invention creatively designs a two-step cascade device with a specific structure and connection relationship for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis. This is a two-step cascade system combining electrocatalysis and thermal catalysis to convert crude acetylene into high-carbon ester products. This cascade process not only helps to reduce carbon emissions, but also facilitates the upgrading of low-value acetylene, providing a promising way to improve the commercial value and environmental value of the acetylene industry.

[0064] The two-step cascade device combining electrocatalysis and thermal catalysis provided by the present invention utilizes the H and H generated by the anode under voltage drive. + , in the cathode chamber of the electrolytic cell, bicarbonate is converted into CO2 in situ, and CO2 is electroreduced to generate CO and OH - The CO2 in the crude acetylene gas is captured and absorbed in the cathode storage chamber through the circulation of the electrolyte to generate bicarbonate, thereby replenishing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode storage chamber and then transported to the acetylene carbonylation reaction storage chamber to undergo acetylene carbonylation reaction to generate high carbon esters such as dimethyl butenedioate, so as to solve the problem of upgrading the utilization of low-value crude acetylene gas and reducing carbon dioxide emissions in the acetylene production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 A schematic diagram of the structure of a two-step cascade device provided by the present invention;

[0066] Figure 1In the figure, 1-electrolytic cell; 11-anode chamber; 111-first end; 112-second end; 12-cation exchange membrane; 13-cathode chamber; 131-third end; 132-fourth end; 14-anode electrode; 15-cathode electrode; 2-gas mass flowmeter; 21-gas mass flowmeter air inlet; 22-gas mass flowmeter air outlet; 3-first peristaltic pump; 31-first peristaltic pump liquid inlet; 32-first peristaltic pump liquid outlet; 4-second peristaltic pump Pump; 41-liquid outlet of the second peristaltic pump; 42-liquid inlet of the second peristaltic pump; 5-anode liquid storage chamber; 51-one end of the anode liquid storage chamber; 52-the other end of the anode liquid storage chamber; 6-cathode liquid storage chamber; 61-one end of the cathode liquid storage chamber; 62-the other end of the cathode liquid storage chamber; 63-crude acetylene gas inlet; 64-cathode liquid storage chamber outlet; 7-acetylene carbonylation reaction liquid storage chamber; 71-carbonylation reaction gas inlet; 72-carbonylation reaction liquid storage chamber outlet. DETAILED DESCRIPTION

[0067] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0068] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0069] There is no particular restriction on the purity of all raw materials in the present invention. The present invention preferably uses analytically pure materials or materials with conventional purity requirements in the field of preparing high carbon ester compounds from acetylene.

[0070] All raw materials and process steps of the present invention, their brands or abbreviations are conventional brands or abbreviations in the art, and each brand or abbreviation is clear and definite in the field of its related use. Those skilled in the art can purchase them from the market or prepare them by conventional methods, or implement them with corresponding equipment according to the brands, abbreviations and corresponding uses.

[0071] The present invention provides a two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, comprising:

[0072] Electrolytic cell;

[0073] A cation exchange membrane disposed in the electrolytic cell;

[0074] The cation exchange membrane is provided with an anode electrode on one side and a cathode electrode on the other side;

[0075] The cation exchange membrane separates the electrolytic cell into a cathode chamber and an anode chamber;

[0076] The anode chamber is provided with an anode chamber liquid inlet and an anode chamber liquid outlet;

[0077] an anode liquid storage device;

[0078] The anode liquid storage device is connected to the anode chamber liquid inlet and the anode chamber liquid outlet respectively;

[0079] The cathode chamber is provided with a cathode chamber liquid inlet and a cathode chamber liquid outlet;

[0080] cathode liquid storage device;

[0081] The cathode liquid storage device is connected to the cathode chamber liquid inlet and the cathode chamber liquid outlet respectively;

[0082] The cathode liquid storage device is connected to a crude acetylene source;

[0083] Acetylene carbonylation reaction unit;

[0084] The acetylene carbonylation reaction device is connected to the cathode liquid storage device.

[0085] In the present invention, the anode liquid storage device is preferably provided with a gas outlet. Specifically, the anode liquid storage device may be an anode liquid storage chamber.

[0086] In the present invention, the anode liquid storage device is preferably provided with an anode liquid storage device liquid inlet pipeline connected to the anode chamber liquid outlet.

[0087] In the present invention, the outlet of the liquid inlet pipeline of the anode liquid storage device is preferably located above the liquid level of the anode liquid storage device.

[0088] In the present invention, the anode liquid storage device is preferably provided with an anode liquid storage device liquid outlet pipeline connected to the anode chamber liquid inlet.

[0089] In the present invention, the inlet of the liquid outlet pipeline of the anode liquid storage device is preferably located below the liquid level of the anode liquid storage device.

[0090] In the present invention, the liquid outlet pipeline of the anode liquid storage device is preferably provided with a first conveying device, which may be a peristaltic pump.

[0091] In the present invention, the cathode liquid storage device is preferably provided with a cathode liquid storage device liquid inlet pipeline connected to the cathode chamber liquid outlet. Specifically, the cathode liquid storage device can be a cathode liquid storage cavity.

[0092] In the present invention, the outlet of the liquid inlet pipeline of the cathode liquid storage device is preferably located above the liquid level of the cathode liquid storage device.

[0093] In the present invention, the cathode liquid storage device is preferably provided with a cathode liquid storage device liquid outlet pipeline connected to the cathode chamber liquid inlet.

[0094] In the present invention, the inlet of the liquid outlet pipeline of the cathode liquid storage device is preferably located below the liquid level of the cathode liquid storage device.

[0095] In the present invention, the cathode liquid storage device liquid outlet pipeline is preferably provided with a second conveying device, which may be a peristaltic pump.

[0096] In the present invention, the cathode liquid storage device is preferably provided with a crude acetylene intake pipeline.

[0097] In the present invention, the inlet of the crude acetylene intake pipeline is preferably connected to a crude acetylene source.

[0098] In the present invention, the outlet of the crude acetylene inlet pipeline is preferably located below the liquid level of the cathode liquid storage device.

[0099] In the present invention, the two-step cascade device preferably further comprises an electrochemical workstation.

[0100] In the present invention, the electrochemical workstation is preferably connected to the anode electrode and the cathode electrode respectively.

[0101] In the present invention, the cathode liquid storage device is preferably provided with a mixed gas outlet.

[0102] In the present invention, the mixed gas outlet is preferably located above the liquid level of the cathode liquid storage device.

[0103] In the present invention, the mixed gas outlet is preferably connected to the gas inlet of the acetylene carbonylation reaction device. Specifically, the gas inlet of the acetylene carbonylation reaction device is preferably located below the liquid level in the acetylene carbonylation reaction device.

[0104] In the present invention, the acetylene carbonylation reaction device is preferably provided with a gas outlet. Specifically, the acetylene carbonylation reaction device can be an acetylene carbonylation reaction liquid storage chamber. The gas outlet is preferably located above the liquid level in the acetylene carbonylation reaction device.

[0105] In the present invention, the material of the anode electrode preferably includes a metal porous material or a metal porous material loaded with iridium oxide.

[0106] In the present invention, the material of the cathode electrode preferably includes catalyst-loaded carbon cloth or catalyst-loaded carbon felt.

[0107] In the present invention, the catalyst preferably includes one or more of nickel, iron, zinc, silver and porous noble metals, more preferably nickel, iron, zinc, silver or porous noble metals.

[0108] In the present invention, the electrolyte in the cathode chamber is preferably a bicarbonate solution.

[0109] In the present invention, the electrolyte in the anode chamber is preferably a sulfuric acid solution.

[0110] In the present invention, the acetylene carbonylation reaction device is preferably provided with an acetylene carbonylation solution.

[0111] The present invention provides a method for preparing high carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, comprising the following steps:

[0112] 1) Under the condition of power supply, the electrochemical reaction is carried out. Under the action of the anode electrode, the water in the anode electrolyte in the anode chamber is decomposed into H + and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, the HCO3 in the cathode electrolyte in the cathode chamber - With H + Generate CO2, and then conduct CO2 electroreduction reaction to obtain CO, H2, OH - and a gas-liquid mixture of a catholyte;

[0113] 2) The crude acetylene gas is introduced into the gas-liquid mixture obtained in the above step, and the CO2 in the crude acetylene gas is absorbed to obtain a mixed gas containing C2H2 and CO. The mixed gas is then introduced into an acetylene carbonylation solution, and C2H2 and CO are catalyzed to undergo acetylene carbonylation reaction to obtain high carbon ester compounds.

[0114] The present invention firstly performs an electrochemical reaction under the condition of power supply. Under the action of the anode electrode, the water in the anode electrolyte in the anode chamber is decomposed into H + and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, the HCO3 in the cathode electrolyte in the cathode chamber - With H + Generate CO2, and then conduct CO2 electroreduction reaction to obtain CO, H2, OH - and a gas-liquid mixture of a catholyte.

[0115] In the present invention, the anolyte is preferably a dilute sulfuric acid solution.

[0116] In the present invention, the cathode electrolyte is preferably a saturated bicarbonate solution.

[0117] In the present invention, the volume ratio of C2H2 and CO2 in the crude acetylene gas is preferably (20-1): (1-20), more preferably (16-5): (5-16), and more preferably (12-9): (9-12).

[0118] In the present invention, after the gas-liquid mixture absorbs CO2 in the crude acetylene gas, it is preferably returned to the cathode chamber to carry out the reaction in step 1).

[0119] The present invention then introduces crude acetylene gas into the gas-liquid mixture obtained in the above step, absorbs CO2 in the crude acetylene gas, and obtains a mixed gas containing C2H2 and CO. The mixed gas is then introduced into an acetylene carbonylation solution, and C2H2 and CO are catalyzed to undergo acetylene carbonylation reaction to obtain high-carbon ester compounds.

[0120] In the present invention, the high carbon ester compound is preferably an ester compound having 6 or more carbon atoms.

[0121] In the present invention, the ester compound having carbon atoms greater than or equal to 6 preferably includes one or more of dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate and dipentyl butenedioate, more preferably dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate or dipentyl butenedioate.

[0122] In the present invention, the acetylene carbonylation solution preferably comprises acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt and anhydrous lithium salt.

[0123] In the present invention, the alcohol solvent preferably includes one or more of methanol, ethanol, propanol, butanol and pentanol, and more preferably methanol, ethanol, propanol, butanol or pentanol.

[0124] In the present invention, the palladium salt preferably includes one or more of palladium chloride, palladium bromide and palladium acetate, and more preferably palladium chloride, palladium bromide or palladium acetate.

[0125] In the present invention, the anhydrous lithium salt preferably includes one or more of anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide and anhydrous lithium iodide, and more preferably anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide or anhydrous lithium iodide.

[0126] In the present invention, the volume ratio of acetonitrile to alcohol solvent is preferably (5-100):(1-10), more preferably (25-80):(3-8), and more preferably (45-60):(5-6).

[0127] In the present invention, the volume ratio of acetonitrile to methanesulfonic acid is preferably (5-100):(0.05-1), more preferably (25-80):(0.25-0.8), and more preferably (45-60):(0.45-0.6).

[0128] In the present invention, the mass volume ratio of the palladium salt to acetonitrile is preferably (1-10) mg: (0.5-10) mL, more preferably (3-8) mg: (2-8) mL, and more preferably (5-6) mg: (4-6) mL.

[0129] In the present invention, the mass ratio of the palladium salt to the anhydrous lithium salt is preferably (1-10):(1-10), more preferably (2-8):(2-8), and more preferably (4-6):(4-6).

[0130] The present invention proposes a two-step cascade system combining electrocatalysis and thermal catalysis to convert crude acetylene into high-carbon ester products. First, CO is generated by an electrochemical method with high Faraday efficiency, and then CO and C2H2 in the crude acetylene gas undergo a thermochemical acetylene carbonylation reaction to generate high-carbon esters. Compared with the traditional reverse water-gas shift reaction to produce CO, the electrochemical route to produce CO has significant advantages in production costs, and the method also reduces the dependence on the separation of acetylene and carbon dioxide. This cascade process not only helps to reduce carbon emissions, but also facilitates the upgrading of low-value acetylene, providing a promising way to increase the commercial value of the acetylene industry.

[0131] The present invention is to complete and refine the overall technical solution, better ensure the structure and composition of the two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, and further improve the stability and efficiency of the process of preparing high-carbon ester compounds from crude acetylene. The above-mentioned two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis and the corresponding method may specifically include the following contents:

[0132] A two-step cascade device combining electrocatalysis and thermal catalysis, comprising:

[0133] Electrolytic cell;

[0134] A cation exchange membrane is disposed in the electrolytic cell, and the cation exchange membrane separates the electrolytic cell into a cathode chamber and an anode chamber, wherein under the drive of an applied potential, an oxygen evolution reaction (OER) occurs in the anode chamber to dissociate water molecules into H + , H + Migrate through the cation exchange membrane to the cathode chamber.

[0135] A cathode liquid storage chamber, wherein a crude acetylene gas inlet is provided on the cathode liquid storage chamber, and the crude acetylene gas inlet is suitable for introducing crude acetylene gas; one end of the cathode liquid storage chamber is connected with the third end of the cathode chamber, and the cathode liquid storage chamber is suitable for receiving the second gas-liquid mixture; a cathode liquid storage chamber outlet is provided on the cathode liquid storage chamber, and the cathode liquid storage chamber outlet is suitable for mixing the gas in the second gas-liquid mixture with the original crude acetylene gas in the cathode liquid storage chamber and discharging it; the other end of the cathode liquid storage chamber is connected with the fourth end of the cathode chamber opposite to the third end, and the cathode liquid storage chamber is suitable for transporting the electrolyte in the cathode liquid storage chamber to the cathode chamber, and the electrolyte in the cathode liquid storage chamber contains the liquid in the second gas-liquid mixture;

[0136] an anode liquid storage chamber, one end of which is in communication with the first end of the anode chamber, and the cathode liquid storage chamber is adapted to transport the electrolyte in the anode liquid storage chamber to the anode chamber so that the anode chamber undergoes an oxygen evolution reaction to produce O2 and H + , thereby generating a first gas-liquid mixture, wherein a gas diffusion port is provided on the anode liquid storage chamber;

[0137] The second end of the anode chamber opposite to the first end is connected to the other end of the cathode liquid storage chamber to transport the first gas-liquid mixture to the anode liquid storage chamber, and the gas in the first gas-liquid mixture is output from the gas diffusion port of the anode liquid storage chamber.

[0138] An acetylene carbonylation reaction liquid storage chamber, wherein the carbonylation reaction gas inlet of the acetylene carbonylation reaction liquid storage chamber is connected with the cathode liquid storage chamber outlet, and the carbonylation reaction liquid storage chamber is suitable for the CO and C2H2 in the mixed gas input into the acetylene carbonylation reaction liquid storage chamber to undergo acetylene carbonylation reaction to generate the target products such as dimethyl butenedioate, diethyl butenedioate, dibutyl butenedioate and other high carbon ester products, and the unreacted gas is discharged through the outlet arranged on the acetylene carbonylation reaction liquid storage chamber.

[0139] Specifically, the device further includes:

[0140] The first peristaltic pump is disposed between the anode liquid storage cavity and the anode chamber, and is used for pumping the electrolyte in the anode liquid storage cavity into the anode chamber through the first peristaltic pump.

[0141] Specifically, the device further includes:

[0142] The second peristaltic pump is disposed between the cathode liquid storage chamber and the cathode chamber, and is used to pump the electrolyte in the cathode liquid storage chamber into the cathode chamber through the second peristaltic pump.

[0143] Specifically, the device further includes:

[0144] A gas mass flow meter is connected to the crude acetylene gas inlet of the cathode liquid storage chamber, and is used to control the gas flow rate of the crude acetylene gas and transport the crude acetylene gas to the cathode liquid storage chamber.

[0145] The volume ratio of C2H2 and CO2 in the crude acetylene gas is (20~1):(1~20).

[0146] Specifically, the device further includes:

[0147] The anode electrode is arranged between the anode chamber and the cation exchange membrane, and is used for being electrically connected to the anode of the electrochemical workstation.

[0148] Specifically, in the device, the material of the anode electrode includes a metal porous material or a titanium mesh loaded with iridium oxide.

[0149] Specifically, the device further includes:

[0150] The cathode electrode is disposed between the cathode chamber and the cation exchange membrane and is used for being electrically connected to the cathode of the electrochemical workstation.

[0151] Specifically, in the device, the material of the cathode electrode is any catalyst-loaded carbon cloth or carbon felt, and the catalyst includes: nickel, iron, zinc, silver nanoparticles or porous precious metals.

[0152] Specifically, in the device, the electrolyte in the cathode liquid storage chamber is a saturated bicarbonate solution, and the electrolyte in the anode liquid storage chamber is a sulfuric acid solution.

[0153] Specifically, in the device, the solution in the acetylene carbonylation reaction liquid storage chamber is acetonitrile, alcohols, methanesulfonic acid, palladium salt, and anhydrous lithium salt.

[0154] Specifically, the volume of the acetonitrile is 5 to 100 mL, the volume of the alcohol is 1 to 10 mL, the types of the alcohol include methanol, ethanol, propanol, butanol, and pentanol, the volume of the methanesulfonic acid is 0.05 to 1 mL, the mass of the palladium salt is 10 to 100 mg, the type of the palladium salt is palladium chloride, palladium bromide, and palladium acetate, the mass of the anhydrous lithium salt is 10 to 100 mg, and the types of the anhydrous lithium salt are anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide, and anhydrous lithium iodide.

[0155] Specifically, the device, wherein

[0156] The cathode chamber absorbs and utilizes CO2 in the crude acetylene mixed gas and converts it into CO, so as to achieve the reduction of carbon dioxide emissions in the crude acetylene gas; the solution in the acetylene carbonylation reaction storage chamber reacts so that the carbon monoxide and acetylene undergo acetylene carbonylation reaction and are converted into dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate, and dipentyl butenedioate.

[0157] Further:

[0158] A novel two-step cascade device combining electrocatalysis and thermocatalysis, comprising:

[0159] Electrolytic cell.

[0160] The cationic membrane is arranged in the electrolytic cell, and the cationic membrane is configured to separate the electrolytic cell into a cathode chamber and an anode chamber, wherein, driven by an applied potential, an oxygen evolution reaction (OER) occurs at the anode to dissociate water molecules into H + , H + Migrate to the cathode through the proton exchange membrane. In the cathode channel, bicarbonate first reacts with dissociated H + Combined to form CO2, which is then reduced in situ on the cathode catalyst to form CO. The OH generated at the cathode - CO2 can be captured from crude acetylene gas while replenishing the consumed HCO3 - .

[0161] A cathode liquid storage chamber is provided with a crude acetylene gas inlet, one end of the cathode liquid storage chamber is connected with the third end, the cathode liquid storage chamber outlet is suitable for mixing the gas in the second gas-liquid mixture with the original crude acetylene gas in the cathode liquid storage chamber and discharging it, the other end of the cathode liquid storage chamber is connected with the fourth end of the cathode chamber opposite to the third end, and the cathode liquid storage chamber is suitable for inputting the electrolyte in the cathode liquid storage chamber into the cathode chamber so that bicarbonate is electro-reduced to generate CO in the cathode chamber to generate the second gas-liquid mixture.

[0162] an anode liquid storage chamber, one end of which is in communication with the first end of the anode chamber, and the anode liquid storage chamber is adapted to transport the electrolyte in the anode liquid storage chamber to the anode chamber so that the anode chamber undergoes an oxygen evolution reaction to produce O2 and H + , thereby generating a first gas-liquid mixture, and a gas diffusion port is provided on the anode liquid storage chamber.

[0163] The second end of the anode chamber opposite to the first end is connected to the other end of the cathode liquid storage chamber to transport the first gas-liquid mixture to the anode liquid storage chamber, and the gas in the first gas-liquid mixture is discharged from the gas diffusion port of the anode liquid storage chamber.

[0164] An acetylene carbonylation reaction liquid storage chamber, wherein the carbonylation reaction gas inlet of the acetylene carbonylation reaction liquid storage chamber is connected with the cathode liquid storage chamber outlet, and the carbonylation reaction liquid storage chamber is suitable for the CO and C2H2 in the mixed gas input into the acetylene carbonylation reaction liquid storage chamber to undergo acetylene carbonylation reaction to generate the target product dimethyl butenedioate and other high carbon ester products, and the unreacted gas is discharged through the outlet arranged on the acetylene carbonylation reaction liquid storage chamber.

[0165] According to an embodiment of the present invention, the electrocatalytic device further comprises: a first peristaltic pump disposed between the anode liquid storage chamber and the anode chamber, and configured to pump the electrolyte in the anode liquid storage chamber into the anode chamber via the first peristaltic pump.

[0166] According to an embodiment of the present invention, the electrocatalytic device further comprises: a second peristaltic pump disposed between the cathode liquid storage chamber and the cathode chamber, for pumping the electrolyte in the cathode liquid storage chamber into the cathode chamber through the second peristaltic pump.

[0167] According to an embodiment of the present invention, the electrocatalytic device further comprises: a gas mass flow meter connected to the crude acetylene gas inlet of the cathode liquid storage chamber, for controlling the gas flow rate of the crude acetylene gas and delivering the crude acetylene gas to the cathode liquid storage chamber.

[0168] According to an embodiment of the present invention, the electrocatalytic device further comprises: an anode electrode, which is disposed between the anode chamber and the cation exchange membrane and is used to be electrically connected to the anode of the electrochemical workstation.

[0169] According to an embodiment of the present invention, in the electrocatalytic device, the material of the anode electrode includes a metal porous material or a titanium mesh loaded with iridium oxide.

[0170] According to an embodiment of the present invention, the electrocatalytic device further comprises: a cathode electrode, which is disposed between the cathode chamber and the cation exchange membrane and is used for being electrically connected to the cathode of the electrochemical workstation.

[0171] According to an embodiment of the present invention, in the electrocatalytic device, the material of the cathode electrode is any catalyst-loaded carbon cloth or carbon felt, and the catalyst includes: nickel, iron, zinc, silver nanoparticles or porous precious metals.

[0172] According to an embodiment of the present invention, in the electrocatalytic device, the electrolyte in the cathode liquid storage chamber is a saturated bicarbonate solution, and the electrolyte in the anode liquid storage chamber is a sulfuric acid solution.

[0173] According to an embodiment of the present invention, in the thermal catalytic device, the solution in the acetylene carbonylation reaction storage chamber is acetonitrile, methanol, methanesulfonic acid, palladium bromide, and anhydrous lithium bromide. The volume of the acetonitrile is 5~100 mL, the volume of the alcohol is 1~10 mL, the types of the alcohols include methanol, ethanol, propanol, butanol, and amyl alcohol, the volume of the methanesulfonic acid is 0.05~1 mL, the mass of the palladium salt is 10~100 mg, the type of the palladium salt is palladium chloride, palladium bromide, and palladium acetate, the mass of the anhydrous lithium salt is 10~100 mg, and the types of the anhydrous lithium salt are anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide, and anhydrous lithium iodide.

[0174] According to an embodiment of the present invention, in the electrocatalytic device, CO2 in the mixed gas is absorbed and utilized in the cathode chamber to achieve carbon dioxide emission reduction in the crude acetylene gas; in the thermal catalytic device, the solution in the acetylene carbonylation reaction storage chamber reacts so that carbon monoxide and acetylene undergo acetylene carbonylation reaction to produce dimethyl butene ester, thereby achieving upgraded utilization of the crude acetylene gas.

[0175] According to an embodiment of the present invention, a two-step cascade device combining electrocatalysis and thermocatalysis is provided, which utilizes the H and H generated by the anode under voltage drive. + , in the cathode chamber of the electrolytic cell, bicarbonate is converted into CO2 in situ, and CO2 is electroreduced to generate CO and OH - The CO2 in the crude acetylene gas is captured and absorbed in the cathode storage chamber through the circulation of the electrolyte to generate bicarbonate, thereby replenishing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode storage chamber and then transported to the acetylene carbonylation reaction storage chamber to undergo acetylene carbonylation reaction to generate high carbon esters such as dimethyl butenedioate, so as to solve the problem of upgrading the utilization of low-value crude acetylene gas and reducing carbon dioxide emissions in the acetylene production process.

[0176] See also Figure 1 , Figure 1 The schematic diagram of the structure of the two-step cascade device provided by the present invention. Among them, 1-electrolytic cell; 11-anode chamber; 111-first end (anode chamber liquid inlet); 112-second end (anode chamber liquid outlet); 12-cation exchange membrane; 13-cathode chamber; 131-third end (cathode chamber liquid inlet); 132-fourth end (cathode chamber liquid outlet); 14-anode electrode; 15-cathode electrode; 2-gas mass flowmeter; 21-gas mass flowmeter air inlet; 22-gas mass flowmeter air outlet; 3-first peristaltic pump (first conveying device); 31-first peristaltic pump liquid inlet; 32-first peristaltic pump liquid outlet; 4-second peristaltic pump (second conveying device); 41-second peristaltic pump liquid outlet; 42-second peristaltic pump liquid inlet; 5-anode liquid storage chamber (anode liquid storage device); 51-one end of the anode liquid storage chamber (liquid outlet pipeline of the anode liquid storage device); 52-the other end of the anode liquid storage chamber (liquid inlet pipeline of the anode liquid storage device); 6-cathode liquid storage chamber (cathode liquid storage device); 61-one end of the cathode liquid storage chamber (liquid outlet pipeline of the cathode liquid storage device); 62-the other end of the cathode liquid storage chamber (liquid inlet pipeline of the cathode liquid storage device); 63-crude acetylene gas inlet (crude acetylene inlet pipeline); 64-cathode liquid storage chamber outlet (mixed gas outlet); 7-acetylene carbonylation reaction liquid storage chamber (acetylene carbonylation reaction device); 71-carbonylation reaction gas inlet (gas inlet of the acetylene carbonylation reaction device); 72-carbonylation reaction liquid storage chamber outlet (gas outlet of the acetylene carbonylation reaction device).

[0177] The present invention proposes a two-step cascade system combining electrocatalysis and thermal catalysis to convert crude acetylene into high-carbon ester products. This cascade process not only helps reduce carbon emissions, but also facilitates the upgrading of low-value acetylene, providing a promising way to improve the commercial and environmental value of the acetylene industry.

[0178] like Figure 1As shown, the electrocatalytic device may include: an electrolytic cell 1, a cation exchange membrane 12, an anode liquid storage chamber 5, a cathode liquid storage chamber 6, and an acetylene carbonylation reaction liquid storage chamber 7.

[0179] The electrolytic cell 1 is the main structure of the electrocatalytic device, which is used to perform electroreduction of bicarbonate to generate CO, and the CO2 in the crude acetylene gas is converted into CO by the OH produced in the electrolytic cell 1. - The crude acetylene gas may be the crude acetylene gas actually produced in the industrial production of acetylene or a mixed gas of C2H2 and CO2 in a certain proportion.

[0180] The acetylene carbonylation reaction liquid storage chamber 7 is the main structure of the thermal catalytic device, which is used to carry out acetylene carbonylation reaction to produce a series of high-carbon ester products such as dimethyl succinate. The gas undergoing acetylene carbonylation reaction is C2H2 and CO in the mixed gas output from the cathode liquid storage chamber outlet to the acetylene carbonyl reaction liquid storage chamber.

[0181] The cation exchange membrane 12 is disposed in the electrolytic cell 1, and the electrolytic cell 1 is divided into an anode chamber 11 and a cathode chamber 13. The anode chamber 11 undergoes an oxygen evolution reaction (OER), which dissociates water molecules into H + , H + Migrate to cathode chamber 13 through cation exchange membrane 12. In cathode chamber 13, bicarbonate first reacts with dissociated H + Combined to form CO2, which is then reduced in situ on the cathode catalyst to form CO. The OH produced in the cathode chamber 13 - CO2 can be captured from crude acetylene gas while replenishing the consumed HCO3 - The anode chamber 11 is provided with a first end 111 and a second end 112 opposite to the first end 111 . The cathode chamber 13 is provided with a third end 131 and a fourth end 132 opposite to the third end 131 .

[0182] One end 61 of the cathode liquid storage chamber 6 is connected to the liquid inlet 42 of the second peristaltic pump 4, and the liquid outlet 41 of the second peristaltic pump 4 is connected to the third end 131 of the cathode chamber 13. The cathode liquid storage chamber 6 is provided with a crude acetylene gas inlet 63, which is suitable for introducing crude acetylene gas. The cathode liquid storage chamber 6 is suitable for transporting the electrolyte in the cathode liquid storage chamber 6 to the cathode chamber 13, so that a bicarbonate electroreduction reaction occurs in the cathode chamber 13, thereby generating a second gas-liquid mixture in the cathode chamber 13, and generating OH at the same time. - , the generated OH - CO2 in the crude acetylene gas can be captured in the cathode liquid storage chamber 6. That is, a bicarbonate electroreduction reaction occurs in the cathode chamber 13 to generate a second gas-liquid mixture, which is then transported back to the cathode liquid storage chamber 6. The OH generated in the cathode chamber 13 is -CO2 in the crude acetylene gas will be captured in the cathode liquid storage chamber 6, thereby replenishing the HCO3 consumed in the cathode chamber 13 to a certain extent. - The gas of the second gas-liquid mixture includes CO and H2.

[0183] One end 51 of the anode liquid storage chamber 5 is communicated with the liquid inlet 31 of the first peristaltic pump 3, the liquid outlet 32 ​​of the first peristaltic pump 3 is communicated with the first end 111 of the anode chamber 11, and the other end 52 of the anode liquid storage chamber 5 is communicated with the second end 112 of the anode chamber 11 opposite to the first end. The anode liquid storage chamber 5 is suitable for receiving the first gas-liquid mixture generated in the anode chamber 11. A gas diffusion port is provided on the anode liquid storage chamber 5, and the gas diffusion port is suitable for discharging the gas in the first gas-liquid mixture. The anode liquid storage chamber 5 is also suitable for inputting the electrolyte of the anode liquid storage chamber into the anode chamber 11. The electrolyte in the anode liquid storage chamber 5 contains the electrolyte stored in advance and the liquid in the first gas-liquid mixture.

[0184] According to an embodiment of the present invention, the electrolyte in the cathode liquid storage chamber 6 is input into the cathode chamber 13, and the solution in the cathode chamber reacts to generate a second gas-liquid mixture, and the second gas-liquid mixture contains CO, H2 and the electrolyte.

[0185] According to an embodiment of the present invention, the other end 62 of the cathode liquid storage chamber 6 is connected to the fourth end 132 of the cathode chamber 13 opposite to the third end, so as to transport the second gas-liquid mixture into the cathode liquid storage chamber 6 to realize the circulation of the electrolyte.

[0186] According to an embodiment of the present invention, a cathode liquid storage chamber gas outlet 64 is also provided in the cathode liquid storage chamber 6, and the cathode liquid storage chamber gas outlet 64 can be used to mix the gas in the second gas-liquid mixture with the original crude acetylene gas in the cathode liquid storage chamber and output it from the cathode liquid storage chamber gas outlet to the acetylene carbonylation reaction liquid storage chamber 7, and the CO and C2H2 in the output mixed gas undergo acetylene carbonylation reaction in the acetylene carbonylation reaction liquid storage chamber 7 to generate a series of high-carbon ester products such as dimethyl butene.

[0187] It should be understood that Figure 1 The structure shown is only an example of the embodiment of the present invention to help those skilled in the art understand the technical content of the present invention. Figure 1 The anode liquid storage chamber 5, cathode liquid storage chamber 6 and acetylene carbonylation reaction liquid storage chamber 7 are shown in the shape of a box, but it does not mean that the components of the present invention are limited to Figure 1 In some embodiments of the present invention, the anode liquid storage chamber 5, the cathode liquid storage chamber 6 and the acetylene carbonylation reaction liquid storage chamber 7 can also be any component such as a storage tank or a liquid storage chamber that can store and circulate electrolyte.

[0188] Similarly, the connection mode between the anode liquid storage chamber 5, the cathode liquid storage chamber 6 and the electrolytic cell 1, and the connection mode between the acetylene carbonylation reaction liquid storage chamber 7 and the cathode liquid storage chamber 6 are not limited. In some embodiments of the present invention, they can be any connection mode that can play a role in gas-liquid circulation, such as hard pipes, plastic hoses, silicone tubes, pneumatic joints, etc. According to the embodiment of the present invention, when the crude acetylene gas is to be treated, the crude acetylene gas is input into the cathode liquid storage chamber at a certain flow rate through the gas mass flowmeter 2, and the second gas-liquid mixture generated in the cathode chamber 13 is transported into the cathode liquid storage chamber 6 through the other end 62 of the cathode liquid storage chamber 6. The crude acetylene gas and the gas in the second gas-liquid mixture are mixed in the cathode liquid storage chamber 6 and output to the acetylene carbonylation reaction liquid storage chamber 7 together.

[0189] According to an embodiment of the present invention, a voltage is applied to the electrolytic cell 1, and OER occurs in the anode chamber 11, dissociating water molecules into H + , H + Migrate to cathode chamber 13 through cation exchange membrane 12. H2O in the electrolyte in anode chamber 11 reacts as shown in formula (I) on the anode side to generate a first gas-liquid mixture. The reaction of formula (I) is as follows:

[0190] 2H2O-4e - →4H + +O2 (Ⅰ);

[0191] At this time, the gas components in the first gas-liquid mixture only contain O2 gas. The first gas-liquid mixture flows out through the second end 112 of the anode chamber 11 opposite to the first end and enters the anode liquid storage chamber 5, and the gas components in the mixture are discharged through the gas diffusion port provided on the anode liquid storage chamber 5. The electrolyte in the anode liquid storage chamber 5 enters the anode chamber 11 through the first end 111 of the anode chamber 11, and is transported back to the anode liquid storage chamber 5 through the second end 112 of the anode chamber 11 opposite to the first end, and the above process is repeated, thereby realizing the circulation of the electrolyte.

[0192] According to an embodiment of the present invention, H2O in the anode chamber 11 undergoes OER to generate H under the drive of voltage as shown in formula (I). + , H + The crude acetylene gas enters the cathode chamber 13 through the cation exchange membrane; the crude acetylene gas is input into the cathode storage chamber 6 through the crude acetylene gas inlet 63 of the cathode storage chamber 6, and the electrolyte in the cathode storage chamber 6 is input into the cathode chamber 13, and the HCO3 in the electrolyte - and H migrated from the anode chamber 11 + Combined with the in-situ generation of CO2, further CO2 electroreduction reactions such as formula (II) and formula (III) occur, and OH is generated at the same time. -The electrolyte in the cathode chamber 13 is transported back to the cathode liquid storage chamber 6 through the fourth end 132 of the cathode chamber 13 opposite to the third end, and the CO2 in the crude acetylene gas in the cathode liquid storage chamber 6 is converted into OH - The capture reaction occurs as shown in formula (IV), generating HCO3 - , so that the HCO3 consumed in the cathode chamber 13 can be - Here, the cathode chamber 13 undergoes a bicarbonate electroreduction reaction to generate OH - It is used as a medium for capturing CO2 in crude acetylene gas. During the power-on process, there will always be OH - It is dissociated, so no other capture media is needed, avoiding the energy-intensive capture media regeneration step in the CO2 capture process; at this time, the gas components of the second gas-liquid mixture include H2 and CO in addition to CO2 gas, so as to realize the utilization of CO2 in the crude acetylene gas, solving the problem that the crude acetylene gas is difficult to directly undergo CO2 electro-reduction reaction; and C2H2 in the crude acetylene gas in addition to CO2 does not react with the electrolyte. After the second gas-liquid mixture enters the cathode storage chamber 6, the gas in the second gas-liquid mixture mixes with the original crude acetylene gas in the cathode storage chamber and is output from the gas outlet 64 of the cathode storage chamber 6 to the acetylene carbonylation reaction storage chamber 7 to undergo acetylene carbonylation reaction.

[0193] Furthermore, CO and C2H2 in the mixed gas output to the acetylene carbonylation reaction liquid storage chamber 7 undergo acetylene carbonylation reaction under the action of the carbonylation solution to generate dimethyl butenedioate (C6H8O4), as shown in formula (V), diethyl butenedioate (C8H 12 O4), such as formula (VI), dipropyl butenedioate (C 10 H 16 O4), such as formula (VII), dibutyl butyl ester (C 12 H 20 O4), such as formula (VIII), dipentyl butenedioate (C 14 H 24 O4), as shown in formula (IX). The relevant reactions are as follows:

[0194] HCO3 - +H + →CO2+H2O(Ⅱ)

[0195] CO2+H2O+2e - →CO+H2+2OH - (III),

[0196] CO2+OH - →HCO3 - (IV),

[0197] C2H2+CO+CH3OH→C6H8O4 (V),

[0198] C2H2+CO+CH3CH2OH→C8H 12 O4(VI),

[0199] C2H2+CO+CH3CH2CH2OH→C 10 H 16 O4(VII),

[0200] C2H2+CO+CH3CH2CH2CH2OH→C 12 H 20 O4(VIII),

[0201] C2H2+CO+CH3CH2CH2CH2CH2CH2OH→C 14 H 24 O4 (IX).

[0202] The present invention can also control the magnitude of the applied voltage to control H + and OH - The ion concentration can be regulated to adjust the concentration of generated CO and indirectly regulate the amount of ester products generated.

[0203] In the present invention, the O2 generated by the OER in the anode chamber 11 is mixed with the electrolyte in the anode chamber 11 to form a first gas-liquid mixture, and the first gas-liquid mixture flows back to the anode liquid storage chamber 5 through the connection between the second end 112 of the anode chamber 11 opposite to the first end and the other end 52 of the anode liquid storage chamber 5, and the gas in the first gas-liquid mixture is discharged through the gas diffusion port provided on the anode liquid storage chamber 5. The anode electrolyte from which the gas is separated can continue to participate in the circulation process to ensure the stable progress of the electrochemical reaction.

[0204] According to an embodiment of the present invention, the electrocatalytic device may further include: a first peristaltic pump, disposed between the anode liquid storage chamber and the anode chamber, for pumping the electrolyte in the anode liquid storage chamber into the anode chamber through the first peristaltic pump.

[0205] Combination Figure 1 As shown, the first peristaltic pump 3 is placed between the anode liquid storage chamber 5 and the anode chamber 11 , the liquid inlet 31 of the first peristaltic pump 3 is connected to one end 51 of the anode liquid storage chamber 5 , and the liquid outlet 32 ​​of the first peristaltic pump 3 is connected to the first end 111 of the anode chamber 11 .

[0206] Under the action of the first peristaltic pump 3, the electrolyte in the anode liquid storage chamber 5 can be pumped into the anode chamber 11 through one end 51 of the anode liquid storage chamber 5 through the first peristaltic pump 3. By adjusting the working state of the first peristaltic pump 3, the flow rate of the electrolyte pumped into the anode chamber 11 can be adjusted.

[0207] According to an embodiment of the present invention, the electrocatalytic device may further include: a second peristaltic pump, disposed between the cathode liquid storage chamber and the cathode chamber, for pumping the electrolyte in the cathode liquid storage chamber into the cathode chamber through the second peristaltic pump.

[0208] like Figure 1 As shown, the second peristaltic pump 4 is arranged between the cathode liquid storage chamber 6 and the cathode chamber 13 , the liquid inlet 42 of the second peristaltic pump 4 is connected to one end 61 of the cathode liquid storage chamber 6 , and the liquid outlet 41 of the second peristaltic pump 4 is connected to the third end 131 of the cathode chamber 13 .

[0209] Under the action of the second peristaltic pump 4, the electrolyte in the cathode liquid storage chamber 6 can be pumped into the cathode chamber 13 through the second peristaltic pump 4 through one end 61 of the cathode liquid storage chamber 6. By adjusting the working state of the second peristaltic pump 4, the flow rate of the electrolyte pumped into the cathode chamber 13 can be adjusted, thereby regulating the concentration of generated CO. Among them, the electrolyte in the cathode liquid storage chamber 6 contains the liquid in the second gas-liquid mixture generated by the reaction in the cathode chamber. The electrolyte in the anode liquid storage chamber 5 contains the liquid in the first gas-liquid mixture generated by the reaction in the anode chamber.

[0210] It should be noted that the above-mentioned first peristaltic pump 3 and second peristaltic pump 4 only illustrate the process of pumping electrolyte. According to actual needs, they can be replaced by any fluid delivery device that can control the flow rate of the fluid, such as: plunger pump, diaphragm pump, etc. The driving mode of the pump can also be any mode that can meet the driving requirements, including electric and pneumatic.

[0211] In addition, the number and connection positions of the above-mentioned first peristaltic pump 3 and the second peristaltic pump 4 are also schematic. In some embodiments of the present invention, a fluid transport device can be added between the anode chamber 11 and the anode liquid storage chamber 5 to regulate the circulation of the first gas-liquid mixture; a fluid transport device can also be added between the cathode chamber 13 and the cathode liquid storage chamber 6 to regulate the circulation of the second gas-liquid mixture.

[0212] According to an embodiment of the present invention, the electrocatalytic device further comprises: a gas mass flow meter connected to the crude acetylene gas inlet of the cathode liquid storage chamber, for controlling the gas flow rate of the crude acetylene gas and delivering the crude acetylene gas to the cathode liquid storage chamber.

[0213] Combination Figure 1As shown, the gas mass flowmeter 2 may include: an air inlet 21 and an air outlet 22. The air inlet 21 can pass the crude acetylene gas in the cylinder into the gas mass flowmeter 2, and the air outlet 22 is connected to the crude acetylene gas inlet 63 of the cathode liquid storage chamber 6. The air outlet 22 can input the crude acetylene gas passed from the air inlet 21 into the cathode liquid storage chamber 6 through the crude acetylene gas inlet 63 provided on the cathode liquid storage chamber 6. The gas mass flowmeter 2 can control the flow rate of the crude acetylene gas to adjust the gas flow entering the cathode liquid storage chamber 6, thereby regulating the performance of the bicarbonate electroreduction in the electrolytic cell.

[0214] It should be noted that in the embodiment of the present invention, a mass flow meter is used to adjust the flow rate of the mixed gas. It should be understood that the gas flow rate control device is not limited and can be replaced by any device that can control the gas flow rate according to actual needs, such as: a float flow meter, an overflow valve, etc.

[0215] According to an embodiment of the present invention, the electrocatalytic device may further include: an anode electrode, disposed between the anode chamber and the cation exchange membrane, for being electrically connected to an anode of the electrochemical workstation.

[0216] Combination Figure 1 As shown, the anode electrode 14 is disposed on one side of the cation exchange membrane 12 and is away from the first end 111 and the second end 112 of the anode chamber, and can be connected to the anode of the electrochemical workstation. The selection of the anode electrode material determines the overpotential reaction of the anode oxygen precipitation.

[0217] According to an embodiment of the present invention, a titanium mesh loaded with iridium oxide may be used as the material of the anode electrode 14 to provide a driving voltage for the electrolytic cell and participate in the bicarbonate electroreduction process.

[0218] According to an embodiment of the present invention, the anode electrode material may also be a porous metal material.

[0219] It should be understood that the above-mentioned selection of anode electrode materials is only an example, and according to actual needs, it can be replaced with one or more materials such as metal platinum, metal aluminum, etc., and there is no specific requirement for its shape.

[0220] According to an embodiment of the present invention, the electrocatalytic device further comprises: a cathode electrode, which is disposed between the cathode chamber and the cation exchange membrane and is used for being electrically connected to the cathode of the electrochemical workstation.

[0221] Combination Figure 1 As shown, the cathode electrode 15 is disposed on the other side of the cation exchange membrane 12 away from the anode electrode 14 and away from the third end 131 and the fourth end 132 of the cathode chamber, and can be connected to the cathode of the electrochemical workstation.

[0222] According to the embodiment of the present invention, the selection of cathode electrode material is an important factor in determining the electro-reduction effect of the generated bicarbonate, and is also a key factor in determining the concentration of high carbon esters generated by the acetylene carbonylation reaction. The cathode electrode material can use a carbon cloth electrode loaded with a nanoparticle catalyst as the material of the cathode electrode 15, which is used to catalyze CO2 and H2O in the cathode chamber 13 to generate CO and H2.

[0223] In some embodiments of the present invention, the cathode electrode material can be any type of catalyst-loaded carbon cloth or carbon felt, and the catalyst can include: nickel, iron, zinc, silver nanoparticles or porous precious metals. By controlling the type of catalyst, a mixture of CO and H2 in different proportions can also be obtained.

[0224] It should be understood that the above-mentioned selection of cathode electrode materials is only an example, and according to actual needs, those skilled in the art may try any cathode material and catalyst that can meet the conductive chemical requirements.

[0225] According to an embodiment of the present invention, in the electrocatalytic device, the electrolyte in the cathode liquid storage chamber is a saturated bicarbonate solution, and the electrolyte in the anode liquid storage chamber is a dilute sulfuric acid solution.

[0226] According to an embodiment of the present invention, in the thermal catalytic device, the solution in the acetylene carbonylation reaction storage chamber has a ratio of acetonitrile, alcohols, methanesulfonic acid, palladium bromide, and anhydrous lithium bromide.

[0227] Specifically, the volume of the acetonitrile is 5 to 100 mL, the volume of the alcohol is 1 to 10 mL, the types of the alcohol include methanol, ethanol, propanol, butanol, and pentanol, the volume of the methanesulfonic acid is 0.05 to 1 mL, the mass of the palladium salt is 10 to 100 mg, the type of the palladium salt is palladium chloride, palladium bromide, and palladium acetate, the mass of the anhydrous lithium salt is 10 to 100 mg, and the types of the anhydrous lithium salt are anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide, and anhydrous lithium iodide.

[0228] In addition, the present invention has no limitation on the selection of bicarbonate. In the embodiment of the present invention, the electrolyte may be a saturated potassium bicarbonate solution. According to actual needs, a saturated sodium bicarbonate solution or the like (for example only) may also be selected. Any electrolyte that can meet the electrochemical requirements may also be selected.

[0229] According to an embodiment of the present invention, in the electrocatalytic device, CO2 in the crude acetylene gas is utilized in the cathode chamber to achieve carbon dioxide emission reduction in the crude acetylene gas; in the thermal catalytic device, carbon monoxide and acetylene in the acetylene carbonylation reaction storage chamber undergo acetylene carbonylation reaction in the carbonylation solution to generate high-carbon ester products such as dimethyl butene, thereby achieving upgraded utilization of low-value crude acetylene gas.

[0230] According to an embodiment of the present invention, the first end 111 of the anode chamber 11 may be a liquid inlet of the anode chamber, and the second end 112 of the anode chamber 11 may be a liquid outlet of the anode chamber. The third end 131 of the cathode chamber 13 may be a liquid inlet of the cathode chamber, and the fourth end 132 of the cathode chamber 13 may be a liquid outlet of the cathode chamber.

[0231] According to an embodiment of the invention, one end 61 of the cathode liquid storage chamber 6 may be a liquid outlet of the cathode liquid storage chamber, and the other end 62 of the cathode liquid storage chamber 6 may be a liquid inlet of the cathode liquid storage chamber. The crude acetylene gas inlet 63 on the cathode liquid storage chamber 6 serves as a crude acetylene gas inlet output from the mass flow meter, and the cathode liquid storage chamber outlet 64 on the cathode liquid storage chamber 6 is disposed between the liquid inlet and the liquid outlet of the cathode liquid storage chamber.

[0232] According to an embodiment of the present invention, one end 51 of the anode liquid storage chamber 5 may be a liquid outlet of the anode liquid storage chamber, and the other end 52 of the anode liquid storage chamber 5 may be a liquid inlet of the anode liquid storage chamber. The gas diffusion ports of the anode liquid storage chamber are evenly distributed on the cover of the anode liquid storage chamber 5.

[0233] Combination Figure 1 As shown, the electrolyte circulation of the electrocatalytic device and the process of upgrading and utilizing the crude acetylene gas are briefly explained.

[0234] like Figure 1 As shown, the electrocatalytic device may include: an electrolytic cell 1 , a gas mass flow meter 2 , a first peristaltic pump 3 , a second peristaltic pump 4 , an anode liquid storage chamber 5 , and a cathode liquid storage chamber 6 .

[0235] The electrolytic cell 1 is the main structure of the electrocatalytic device. The cation exchange membrane 12 is arranged in the electrolytic cell 1 to transport H generated by the oxygen evolution reaction (OER) in the anode chamber. + , and the electrolytic cell 1 is divided into an anode chamber 11 and a cathode chamber 13. The gas mass flowmeter 2 is used to control the flow rate of the crude acetylene gas entering the cathode storage chamber 6. The first peristaltic pump 3 is arranged between the anode storage chamber 5 and the anode chamber 11, and is used to pump the electrolyte in the anode storage chamber 5 into the anode chamber 11. The second peristaltic pump 4 is arranged between the cathode storage chamber 6 and the cathode chamber 13, and is used to pump the electrolyte absorbed by CO2 in the cathode storage chamber 6 into the cathode chamber 13. The anode storage chamber 5 and the cathode storage chamber 6 are used to store and circulate the electrolyte, respectively.

[0236] In the process of treating the crude acetylene gas to be treated, a certain voltage is applied to the electrocatalytic device through the anode electrode 14 and the cathode electrode 15 in the electrolytic cell 1, and the anode chamber 11 in the electrolytic cell 1 undergoes OER to generate H + and O2, and H +The gas mass flowmeter 2 controls the flow of the crude acetylene gas. The gas inlet 21 of the gas mass flowmeter is connected to the steel cylinder storing the crude acetylene gas. The gas outlet 22 of the gas mass flowmeter 2 is connected to the crude acetylene gas inlet 63 of the cathode liquid storage chamber 6. The crude acetylene gas to be treated is passed through the gas inlet and gas outlet of the gas mass flowmeter 2 and the crude acetylene gas inlet 63 provided on the cathode liquid storage chamber 6 into the cathode liquid storage chamber 6. The second peristaltic pump 4 pumps the electrolyte in the cathode liquid storage chamber 6 from the cathode liquid storage chamber 6 to the cathode liquid storage chamber 6. One end 61 (liquid outlet) of the cathode liquid storage chamber 6 is pumped into the cathode chamber 13 through the liquid inlet 42 and the liquid outlet 41 of the second peristaltic pump 4, and the electrolyte reacts in the cathode chamber 13 (i.e., the above reaction formulas II and III) to generate CO2, a mixed gas of CO and H2, and forms a second gas-liquid mixture with the electrolyte, wherein the CO2 in the crude acetylene gas in the cathode liquid storage chamber 6 is absorbed and converted into bicarbonate and enters the electrolyte, thereby realizing the separation and utilization of CO2 in the crude acetylene gas. The second gas-liquid mixture is transported to the cathode liquid storage chamber 6 through the connection between the second end 132 (liquid outlet of the cathode chamber) of the cathode chamber 13 and the other end 62 (liquid inlet) of the cathode liquid storage chamber 6. The cathode liquid storage chamber gas outlet 63 in the cathode liquid storage chamber 6 is connected to the carbonylation reaction gas inlet 71 of the carbonylation reaction liquid storage chamber 7, so that the gas in the second gas-liquid mixture is mixed with the original crude acetylene gas in the cathode liquid storage chamber and output to the acetylene carbonylation reaction liquid storage chamber 7. The CO and C2H2 in the mixed gas can react with acetylene in the acetylene carbonylation reaction liquid storage chamber 7 to generate a series of high-carbon ester products such as the target product dimethyl butenedioate. Among them, the liquid inlet 42 of the second peristaltic pump 4 is connected to one end 61 (liquid outlet) of the cathode liquid storage chamber, and the liquid outlet 41 of the second peristaltic pump 4 is connected to the third end 131 (liquid inlet of the cathode chamber) of the cathode chamber 13.

[0237] In the cathode chamber 13, under the action of the applied voltage and the cathode catalyst, the solution in the cathode chamber reacts (i.e., the above reaction formula II and reaction formula III), generating a mixed gas of CO, CO2 and H2 with a certain ratio, completing the conversion of CO2. At the same time, by controlling the magnitude of the applied voltage and the type of cathode material catalyst, the concentration of generated CO can be controlled.

[0238] OER occurs in the anode chamber 11 to generate O2, which mixes with the electrolyte in the anode chamber 11 to form a first gas-liquid mixture. The first gas-liquid mixture flows back to the anode storage chamber 5 through the second end 112 of the anode chamber (the liquid outlet of the anode chamber) and the other end 52 (the liquid inlet) of the anode storage chamber 5, and is discharged through the gas diffusion port in the anode storage chamber 5. The electrolyte from which the gas is separated is circulated to provide H + .

[0239] According to an embodiment of the present invention, the anode can be driven by voltage to generate H+ , in the cathode chamber of the electrolytic cell, bicarbonate is converted into CO2 in situ, and CO2 is electroreduced to generate CO and OH - The CO2 in the crude acetylene gas is captured and absorbed in the cathode storage chamber through the circulation of the electrolyte to generate bicarbonate, thereby replenishing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode storage chamber and then transported to the acetylene carbonylation reaction storage chamber for acetylene carbonylation reaction to generate a series of ester products such as dimethyl butenedioate, so as to solve the problem of upgrading the utilization of low-value crude acetylene gas and reducing carbon dioxide emissions in the acetylene production process.

[0240] According to an embodiment of the present invention, pressure may be applied between adjacent components of the electrocatalytic device through a silicone gasket and an external nut to achieve a sealing effect, thereby ensuring that the fluid in the device does not overflow.

[0241] The above content of the present invention provides a two-step cascade device and method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis. The present invention provides a two-step cascade system combining electrocatalysis and thermal catalysis to convert crude acetylene into high-carbon ester products. This cascade process not only helps to reduce carbon emissions, but also facilitates the upgrading of low-value acetylene, providing a promising way to improve the commercial value and environmental value of the acetylene industry.

[0242] The two-step cascade device combining electrocatalysis and thermal catalysis provided by the present invention utilizes the H and H generated by the anode under voltage drive. + , in the cathode chamber of the electrolytic cell, bicarbonate is converted into CO2 in situ, and CO2 is electroreduced to generate CO and OH - The CO2 in the crude acetylene gas is captured and absorbed in the cathode storage chamber through the circulation of the electrolyte to generate bicarbonate, thereby replenishing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode storage chamber and then transported to the acetylene carbonylation reaction storage chamber to undergo acetylene carbonylation reaction to generate high carbon esters such as dimethyl butenedioate, so as to solve the problem of upgrading the utilization of low-value crude acetylene gas and reducing carbon dioxide emissions in the acetylene production process.

[0243] In order to further illustrate the present invention, a two-step cascade device and method for preparing high-carbon ester compounds from crude acetylene combining electrocatalysis and thermal catalysis provided by the present invention are described in detail below in conjunction with embodiments. However, it should be understood that these embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation methods and specific operating processes are given only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention, and the protection scope of the present invention is not limited to the following embodiments.

[0244] Example 1

[0245] This embodiment provides a two-step cascade device combining electrocatalysis and thermal catalysis to prepare high carbon ester compounds from crude acetylene and a corresponding method for preparing high carbon ester compounds from crude acetylene by electrocatalysis and thermal catalysis. The reaction device structure is as follows: Figure 1 shown.

[0246] Specific steps: Connect the electrochemical workstation to the electrocatalytic device and apply 100 mA cm -2 The constant current was set at 20 sccm for the peristaltic pump and 10 sccm for the gas mass flowmeter. The ratio of crude acetylene gas was C2H2:CO2 of 9:1. The reacted gas was connected to a hot catalytic reaction tank. In the hot catalytic tank, the solution in the acetylene carbonylation reaction bottle was 30 mL of acetonitrile, 3 mL of methanol, 0.1 mL of methanesulfonic acid, 40 mg of palladium bromide, and 13 mg of anhydrous lithium bromide. The rotor speed of the magnetic stirrer was set to 400 rpm. The product was collected after reacting at 25 °C for 1 hour.

[0247] The yield of dimethyl butenedioate was measured to be 7.83 mmol / L / h, the selectivity of dimethyl maleate was 65%, and the selectivity of dimethyl fumarate was 35%.

[0248] The above is a detailed introduction to a two-step cascade device and method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method and its core ideas of the present invention, including the best mode, and also enables any technician in the field to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the text of the claims, or if they include equivalent structural elements that are not substantially different from the text of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A method for preparing high carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, characterized in that: The following steps are involved: 1) Under the condition of power supply, the electrochemical reaction is carried out. Under the action of the anode electrode, the water in the anode electrolyte in the anode chamber is decomposed into H + and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, the HCO3 in the cathode electrolyte in the cathode chamber - With H + Generate CO2, and then conduct CO2 electroreduction reaction to obtain CO, H2, OH - and a gas-liquid mixture of a catholyte; 2) The crude acetylene gas is introduced into the gas-liquid mixture obtained in the above step, and the CO2 in the crude acetylene gas is absorbed to obtain a mixed gas containing C2H2 and CO. The mixed gas is then introduced into an acetylene carbonylation solution, and C2H2 and CO are catalyzed to undergo acetylene carbonylation reaction to obtain high carbon ester compounds.

2. The method according to claim 1, characterized in that The anolyte is a dilute sulfuric acid solution; The cathode electrolyte is a saturated bicarbonate solution; The volume ratio of C2H2 and CO2 in the crude acetylene gas is (20-1): (1-20); After the gas-liquid mixture absorbs CO2 in the crude acetylene gas, it returns to the cathode chamber to carry out the reaction in step 1).

3. The method according to claim 1, characterized in that The high carbon ester compound is an ester compound having carbon atoms greater than or equal to 6; The ester compound having carbon atoms greater than or equal to 6 includes one or more of dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate and dipentyl butenedioate; The acetylene carbonylation solution comprises acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt and anhydrous lithium salt; The alcohol solvent includes one or more of methanol, ethanol, propanol, butanol and pentanol; The palladium salt includes one or more of palladium chloride, palladium bromide and palladium acetate.

4. The method according to claim 3, characterized in that The anhydrous lithium salt includes one or more of anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide and anhydrous lithium iodide; The volume ratio of acetonitrile to alcohol solvent is (5-100): (1-10); The volume ratio of acetonitrile to methanesulfonic acid is (5-100): (0.05-1); The mass volume ratio of the palladium salt and acetonitrile is (1-10) mg: (0.5-10) mL; The mass ratio of the palladium salt to the anhydrous lithium salt is (1-10): (1-10).

5. A two-step cascade device combining electrocatalysis and thermal catalysis to produce high carbon ester compounds from crude acetylene, characterized in that: include: Electrolytic cell; A cation exchange membrane disposed in the electrolytic cell; The cation exchange membrane is provided with an anode electrode on one side and a cathode electrode on the other side; The cation exchange membrane separates the electrolytic cell into a cathode chamber and an anode chamber; The anode chamber is provided with an anode chamber liquid inlet and an anode chamber liquid outlet; an anode liquid storage device; The anode liquid storage device is connected to the anode chamber liquid inlet and the anode chamber liquid outlet respectively; The cathode chamber is provided with a cathode chamber liquid inlet and a cathode chamber liquid outlet; cathode liquid storage device; The cathode liquid storage device is connected to the cathode chamber liquid inlet and the cathode chamber liquid outlet respectively; The cathode liquid storage device is connected to a crude acetylene source; Acetylene carbonylation reaction unit; The acetylene carbonylation reaction device is connected to the cathode liquid storage device.

6. The two-step cascade device according to claim 5, characterized in that: The anode liquid storage device is provided with a gas outlet; The anode liquid storage device is provided with an anode liquid storage device liquid inlet pipeline connected to the anode chamber liquid outlet; The outlet of the liquid inlet pipeline of the anode liquid storage device is located above the liquid level of the anode liquid storage device; The anode liquid storage device is provided with an anode liquid storage device liquid outlet pipeline connected to the anode chamber liquid inlet; The inlet of the liquid outlet pipeline of the anode liquid storage device is located below the liquid level of the anode liquid storage device; The liquid outlet pipeline of the anode liquid storage device is provided with a first conveying device.

7. The two-step cascade device according to claim 5, characterized in that: The cathode liquid storage device is provided with a cathode liquid storage device liquid inlet pipeline connected to the cathode chamber liquid outlet; The outlet of the liquid inlet pipeline of the cathode liquid storage device is located above the liquid level of the cathode liquid storage device; The cathode liquid storage device is provided with a cathode liquid storage device liquid outlet pipeline connected to the cathode chamber liquid inlet; The inlet of the liquid outlet pipeline of the cathode liquid storage device is located below the liquid level of the cathode liquid storage device; A second conveying device is arranged on the liquid outlet pipeline of the cathode liquid storage device.

8. The two-step cascade device according to claim 5, characterized in that: The cathode liquid storage device is provided with a crude acetylene intake pipeline; The inlet of the crude acetylene inlet pipeline is connected to a crude acetylene source; The outlet of the crude acetylene inlet pipeline is located below the liquid level of the cathode liquid storage device; The two-step cascade device also includes an electrochemical workstation; The electrochemical workstation is connected to the anode electrode and the cathode electrode respectively.

9. The two-step cascade device according to claim 5, characterized in that: The cathode liquid storage device is provided with a mixed gas outlet; The mixed gas outlet is located above the liquid level of the cathode liquid storage device; The mixed gas outlet is connected to the gas inlet of the acetylene carbonylation reaction device; The acetylene carbonylation reaction device is provided with a gas outlet.

10. The two-step cascade device according to claim 5, characterized in that: The material of the anode electrode includes a metal porous material or a metal porous material loaded with iridium oxide; The material of the cathode electrode includes catalyst-loaded carbon cloth or catalyst-loaded carbon felt; The catalyst includes one or more of nickel, iron, zinc, silver and porous noble metals; The electrolyte in the cathode chamber is a bicarbonate solution; The electrolyte in the anode chamber is a sulfuric acid solution; The acetylene carbonylation reaction device is provided with an acetylene carbonylation solution.

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