A method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis and a two-step cascade device

Abstract

The present invention provides a method for preparing high-carbon ester compounds by combining electrocatalysis and thermocatalysis from crude acetylene, as well as a two-step cascade device. First, an electrochemical reaction is carried out. Under the action of the anode electrode, H in the anolyte in the anode chamber + enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, HCO3 in the catholyte ‑ reacts with H + to generate CO2, and an electroreduction reaction is carried out to obtain a gas-liquid mixture. Finally, the crude acetylene gas is introduced into the gas-liquid mixture. After absorbing CO2, a mixed gas containing C2H2 and CO is obtained, and then it is introduced into an acetylene carbonylation solution for an acetylene carbonylation reaction to obtain high-carbon ester compounds. The preparation method and the two-step cascade system designed by the present invention, which combine electrocatalysis and thermocatalysis, 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, improving the commercial value and environmental value of the acetylene industry.

Description

Technical Field

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

[0002] Acetylene is the simplest unsaturated hydrocarbon and also one of the important chemical raw materials, which can be obtained from natural gas or coal. Acetylene is a key gaseous raw material for producing various organic chemicals and polymers, such as acetaldehyde, benzene, synthetic rubber, polyester plastics, etc. Acetylene is mainly produced by the coal-based calcium carbide method or the partial combustion cracking method of natural gas. However, these processes inevitably produce a large amount of carbon dioxide (CO 2 ) as a by-product, resulting in an increase in carbon emissions, exacerbating the greenhouse effect, complicating the direct downstream utilization of acetylene, and making it difficult to further upgrade acetylene.

[0003] Due to the thermodynamic stability of the CO 2 molecule, it is very difficult to directly perform C-C coupling between acetylene and CO 2 . Therefore, the traditional acetylene upgrading process currently adopted is to convert CO 2 into CO through the reverse water gas shift (RWGS) reaction, and then use highly reactive CO to perform carbonylation with C 2 H 2 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 CO 2 as a raw material, and separating CO 2 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 high pressure, resulting in high energy consumption and high cost.

[0004] Therefore, how to find a more suitable green device for producing high-carbon ester compounds from crude acetylene with low energy consumption and high economic efficiency, and directly convert crude acetylene into high-value products, has become one of the focuses widely concerned by 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 producing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermocatalysis. The two-step cascade device provided by the present invention can solve the problems of difficult utilization of low-value crude acetylene gas and CO 2 emission reduction in the acetylene production process.

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

[0007] Electrolytic cell;

[0008] Cation exchange membrane disposed in the electrolytic cell;

[0009] One side of the cation exchange membrane is provided with an anode electrode, and the other side is provided with a cathode electrode;

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

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

[0012] Anode liquid storage device;

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

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

[0015] Cathode liquid storage device;

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

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

[0018] Acetylene carbonylation reaction device;

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

[0020] Preferably, an air outlet is provided on the anode liquid storage device;

[0021] An anode liquid storage device inlet pipeline connected to the anode chamber outlet is provided on the anode liquid storage device;

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

[0023] An anode liquid storage device outlet pipeline connected to the anode chamber inlet is provided on the anode liquid storage device;

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

[0025] A first conveying device is provided on the anode liquid storage device outlet pipeline.

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

[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] A liquid outlet pipeline of the cathode liquid storage device connected to the liquid inlet of the cathode chamber is provided on the cathode liquid storage device;

[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 provided on the liquid outlet pipeline of the cathode liquid storage device.

[0031] Preferably, a crude acetylene inlet 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 further includes an electrochemical workstation;

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

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

[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 inlet of the acetylene carbonylation reaction device;

[0039] An outlet is provided on the acetylene carbonylation reaction device.

[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 a carbon cloth loaded with a catalyst or a carbon felt loaded with a catalyst;

[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] An acetylene carbonylation solution is provided in the acetylene carbonylation reaction device.

[0046] The present invention also provides a method for synthesizing high-carbon esters from crude acetylene by combining electrocatalysis and thermocatalysis, comprising the following steps:

[0047] 1) An electrochemical reaction is carried out under the condition of power-on. Under the action of the anode electrode, water in the anolyte in the anode chamber decomposes into H + , which enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, HCO 3 - in the catholyte in the cathode chamber reacts with H + to generate CO 2 , and a CO 2 electroreduction reaction is carried out to obtain a gas-liquid mixture containing CO, H 2 , OH - and the catholyte;

[0048] 2) The crude acetylene gas is introduced into the gas-liquid mixture obtained in the above step. After absorbing CO 2 in the crude acetylene gas, a mixed gas containing C 2 H 2 and CO is obtained. Then, the mixed gas is introduced into the acetylene carbonylation solution. After the catalytic acetylene carbonylation reaction of C 2 H 2 and CO, high-carbon esters are obtained.

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

[0050] The catholyte is a saturated bicarbonate solution;

[0051] The volume ratio of C 2 H 2 to CO 2 in the crude acetylene gas is (20~1):(1~20);

[0052] After the gas-liquid mixture absorbs CO 2 in the crude acetylene gas, it returns to the cathode chamber to carry out the reaction in step 1).

[0053] Preferably, the high-carbon esters are esters with carbon atoms greater than or equal to 6;

[0054] The esters with carbon atoms greater than or equal to 6 include one or more of dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate and dipentyl maleate;

[0055] The acetylene carbonylation solution includes acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt and an 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 the acetonitrile to the alcohol solvent is (5 - 100):(1 - 10);

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

[0061] The mass - volume ratio of the palladium salt to the 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 present invention provides a two - step cascade device for synthesizing high - carbon ester compounds from crude acetylene by combining electrocatalysis and thermocatalysis, comprising: an electrolytic cell; a cation - exchange membrane disposed in the electrolytic cell; an anode electrode disposed on one side of the cation - exchange membrane and a cathode electrode disposed on the other side; the cation - exchange membrane divides the electrolytic cell into a cathode chamber and an anode chamber; the anode chamber is provided with an anode chamber inlet and an anode chamber outlet; an anode liquid storage device; the anode liquid storage device is respectively connected to the anode chamber inlet and the anode chamber outlet; the cathode chamber is provided with a cathode chamber inlet and a cathode chamber outlet; a cathode liquid storage device; the cathode liquid storage device is respectively connected to the cathode chamber inlet and the cathode chamber 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 for synthesizing high - carbon ester compounds from crude acetylene by combining electrocatalysis and thermocatalysis, which is a two - step cascade system combining electrocatalysis and thermocatalysis, and converts crude acetylene into high - carbon ester products. This cascade process not only helps to reduce carbon emissions, but also is conducive to 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 provided by the present invention for combining electrocatalysis and thermocatalysis uses the [H+] generated at the anode under voltage drive + to in - situ convert bicarbonate into CO 2 in the cathode chamber of the electrolytic cell, 2 and perform the electro - reduction of CO -and capture and absorb CO in the cathode liquid storage chamber through electrolyte circulation in the crude acetylene gas 2 to generate bicarbonate, thereby supplementing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode liquid storage chamber and then transported to the acetylene carbonylation reaction liquid storage chamber to carry out the acetylene carbonylation reaction to generate high-carbon esters such as dimethyl maleate, so as to solve the problems of upgrading and utilization of low-value crude acetylene gas and carbon dioxide emission reduction in the acetylene production process. Brief Description of the Drawings

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

[0066] Figure 1 In 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 inlet; 22 - gas mass flowmeter outlet; 3 - first peristaltic pump; 31 - first peristaltic pump inlet; 32 - first peristaltic pump outlet; 4 - second peristaltic pump; 41 - second peristaltic pump outlet; 42 - second peristaltic pump inlet; 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 Embodiments

[0067] In order to further understand the present invention, the preferred embodiments of the present invention will be described below in conjunction with examples. However, 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] For all raw materials of the present invention, there is no particular limitation on their sources, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0069] For all raw materials of the present invention, there is no particular limitation on their purity. The present invention preferably adopts analytical pure or the conventional purity requirements in the field of acetylene to high-carbon ester compounds.

[0070] For all raw materials and process procedures of the present invention, their trade names or abbreviations all belong to the conventional trade names or abbreviations in the field. Each trade name or abbreviation is clear and definite in the field of its relevant uses. Those skilled in the art can purchase or prepare them by conventional methods according to the trade name, abbreviation and corresponding uses, or implement them using the corresponding equipment.

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

[0072] An electrolytic cell;

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

[0074] An anode electrode is disposed on one side of the cation exchange membrane, and a cathode electrode is disposed on the other side;

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

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

[0077] An anode liquid storage device;

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

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

[0080] A cathode liquid storage device;

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

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

[0083] An acetylene carbonylation reaction device;

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

[0085] In the present invention, an air outlet is preferably provided on the anode liquid storage device. Specifically, the anode liquid storage device may specifically be an anode liquid storage cavity.

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

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

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

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

[0090] In the present invention, a first conveying device is preferably provided on the liquid outlet pipeline of the anode liquid storage device. Specifically, it can be a peristaltic pump.

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

[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, a liquid outlet pipeline of the cathode liquid storage device connected to the liquid inlet of the cathode chamber is preferably provided on the cathode liquid storage device.

[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, a second conveying device is preferably provided on the liquid outlet pipeline of the cathode liquid storage device. Specifically, it can be a peristaltic pump.

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

[0097] In the present invention, the inlet of the crude acetylene inlet 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 includes 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, a mixed gas outlet is preferably provided on the cathode liquid storage device.

[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 inlet of the acetylene carbonylation reaction device. Specifically, the inlet of the acetylene carbonylation reaction device is preferably located below the liquid level inside the acetylene carbonylation reaction device.

[0104] In the present invention, an outlet is preferably provided on the acetylene carbonylation reaction device. Specifically, the acetylene carbonylation reaction device can be an acetylene carbonylation reaction liquid storage chamber. The outlet is preferably located above the liquid level inside 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 a carbon cloth loaded with a catalyst or a carbon felt loaded with a catalyst.

[0107] In the present invention, the catalyst preferably includes one or more of nickel, iron, zinc, silver, and porous noble metals, and 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, an acetylene carbonylation solution is preferably provided in the acetylene carbonylation reaction device.

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

[0112] 1) Performing an electrochemical reaction under the condition of energization. Under the action of the anode electrode, water in the anode electrolyte in the anode chamber decomposes into H + , and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, HCO 3 - in the cathode electrolyte in the cathode chamber reacts with H + to generate CO 2 , and a CO 2 electroreduction reaction occurs to obtain a gas-liquid mixture containing CO, H 2 , OH - , and the cathode electrolyte;

[0113] 2) Passing the crude acetylene gas into the gas-liquid mixture obtained in the above step. After absorbing CO 2 in the crude acetylene gas, a mixed gas containing C 2 H 2 and CO is obtained. Then, the mixed gas is passed into the acetylene carbonylation solution. After the C 2 H 2 and CO undergo a catalytic acetylene carbonylation reaction, high-carbon ester compounds are obtained.

[0114] The present invention first performs an electrochemical reaction under the condition of energization. Under the action of the anode electrode, water in the anode electrolyte in the anode chamber decomposes into H + , and enters the cathode chamber through the cation exchange membrane. Under the action of the cathode electrode, HCO 3- React with H + to generate CO 2 , and perform the electroreduction reaction of CO 2 to obtain a gas-liquid mixture containing CO, H 2 , OH - and the cathode electrolyte.

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

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

[0117] In the present invention, the volume ratio of C 2 H 2 to CO 2 in the crude acetylene gas is preferably (20~1):(1~20), more preferably (16~5):(5~16), and even more preferably (12~9):(9~12).

[0118] In the present invention, after the gas-liquid mixture absorbs CO 2 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 passes the crude acetylene gas into the gas-liquid mixture obtained in the above step, absorbs CO 2 in the crude acetylene gas, and obtains a mixed gas containing C 2 H 2 and CO. Then, the mixed gas is passed into the acetylene carbonylation solution, and after C 2 H 2 and CO undergo a catalytic acetylene carbonylation reaction, a high-carbon ester compound is obtained.

[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 6 or more carbon atoms preferably includes one or more of dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, and dipentyl maleate, and more preferably dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, or dipentyl maleate.

[0122] In the present invention, the acetylene carbonylation solution preferably includes acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt, and an 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 is 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 is anhydrous lithium fluoride, anhydrous lithium chloride, anhydrous lithium bromide, or anhydrous lithium iodide.

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

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

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

[0130] The present invention proposes a two - step cascade system combining electrocatalysis and thermocatalysis to convert crude acetylene into high - carbon ester products. First, CO is generated electrochemically with high Faraday efficiency, and then CO reacts with C 2 H 2 in the crude acetylene gas to undergo thermochemical acetylene carbonylation reaction to produce high - carbon esters. Compared with the traditional reverse water - gas shift reaction for generating CO, the electrochemical route for generating CO has significant advantages in terms of production cost, and this 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 is beneficial to the upgrading of low - value acetylene, providing a promising way to improve the commercial value of the acetylene industry.

[0131] In order to complete and refine the overall technical solution, better ensure the structure and composition of the two - step cascade device for converting crude acetylene into high - carbon ester compounds by combining electrocatalysis and thermocatalysis, and further improve the stability and efficiency of the process for converting crude acetylene into high - carbon ester compounds, the above - mentioned two - step cascade device for converting crude acetylene into high - carbon ester compounds by combining electrocatalysis and thermocatalysis and its corresponding method specifically may include the following content:

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

[0133] An electrolytic cell;

[0134] A cation exchange membrane disposed within the electrolytic cell, which divides the electrolytic cell into a cathode chamber and an anode chamber. Under the driving of an applied potential, an oxygen evolution reaction (OER) occurs in the anode chamber, dissociating water molecules into H + , H + which migrates through the cation exchange membrane to the cathode chamber.

[0135] A cathode liquid storage chamber is provided with a crude acetylene gas inlet, which is suitable for introducing crude acetylene gas; one end of the cathode liquid storage chamber is communicated with the third end of the cathode chamber. The cathode liquid storage chamber is suitable for receiving the second gas-liquid mixture. The cathode liquid storage chamber is provided with a cathode liquid storage chamber outlet, which is suitable for discharging the gas in the second gas-liquid mixture mixed with the original crude acetylene gas in the cathode liquid storage chamber. The other end of the cathode liquid storage chamber is communicated with the fourth end of the cathode chamber opposite to the third end. The cathode liquid storage chamber is suitable for transporting the electrolyte in the cathode liquid storage chamber to the cathode chamber. 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 communicated with the first end of the anode chamber. The cathode liquid storage chamber is suitable for transporting the electrolyte in the anode liquid storage chamber to the anode chamber so that an oxygen evolution reaction occurs in the anode chamber to generate O 2 and H + , thereby generating a first gas-liquid mixture. The anode liquid storage chamber is provided with a gas dispersion port;

[0137] Wherein, the second end of the anode chamber opposite to the first end is communicated with 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 dispersion port of the anode liquid storage chamber.

[0138] An acetylene carbonylation reaction liquid storage chamber, the carbonylation reaction gas inlet of which is communicated with the cathode liquid storage chamber outlet. The carbonylation reaction liquid storage chamber is suitable for inputting CO and C in the mixed gas into the acetylene carbonylation reaction liquid storage chamber 2 H 2 to carry out an acetylene carbonylation reaction to generate the target products such as dimethyl maleate, diethyl maleate, dibutyl maleate and other high-carbon ester products, and the unreacted gas is discharged through the outlet provided on the acetylene carbonylation reaction liquid storage chamber.

[0139] Specifically, the device further includes:

[0140] A first peristaltic pump is disposed between the anode liquid storage chamber and the anode chamber, and is used to pump the electrolyte in the anode liquid storage chamber into the anode chamber through the first peristaltic pump.

[0141] Specifically, the device further includes:

[0142] A 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 flowmeter is connected to the inlet of the crude acetylene gas 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 into the cathode liquid storage chamber.

[0145] The volume ratio of C 2 H 2 and CO 2 in the crude acetylene gas is (20~1):(1~20).

[0146] Specifically, the device further includes:

[0147] An anode electrode 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.

[0148] Specifically, for 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] A cathode electrode is disposed between the cathode chamber and the cation exchange membrane, and is used to be electrically connected to the cathode of the electrochemical workstation.

[0151] Specifically, for the device, the material of the cathode electrode is a carbon cloth or carbon felt loaded with any kind of catalyst, and the catalyst includes: nickel, iron, zinc, silver nanoparticles or porous noble metals.

[0152] Specifically, for 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, for the described device, the solution in the acetylene carbonylation reaction reservoir is acetonitrile, alcohol, methanesulfonic acid, palladium salt, and anhydrous lithium salt.

[0154] Specifically, the volume of the acetonitrile is 5 - 100 mL, the volume of the alcohol is 1 - 10 mL, the types of the alcohol include methanol, ethanol, propanol, butanol, and pentanol, the volume of the methanesulfonic acid is 0.05 - 1 mL, the mass of the palladium salt is 10 - 100 mg, the types of the palladium salt are 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.

[0155] Specifically, for the described device, wherein,

[0156] CO in the crude acetylene mixed gas is absorbed and utilized in the cathode chamber 2 and converted into CO to achieve carbon dioxide emission reduction in the crude acetylene gas; the solution in the acetylene carbonylation reaction reservoir reacts so that carbon monoxide and acetylene undergo an acetylene carbonylation reaction to be converted into dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, and dipentyl maleate.

[0157] Furthermore:

[0158] A new two - step cascade device combining electrocatalysis and thermocatalysis includes:

[0159] An electrolytic cell.

[0160] A cation exchange membrane, disposed in the electrolytic cell, is configured to divide 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 at the anode, dissociating water molecules into H + , H + which migrates to the cathode through the proton exchange membrane. In the cathode channel, bicarbonate first combines with the dissociated H + to form CO 2 , and then CO 2 is in - situ reduced on the cathode catalyst to form CO. The OH - generated at the cathode can capture CO 2 from the crude acetylene gas, while supplementing the consumed HCO 3 - .

[0161] The cathode liquid storage chamber is provided with a raw acetylene gas inlet. One end of the cathode liquid storage chamber is connected to the third end, and the cathode liquid storage chamber gas outlet is adapted to discharge the gas in the second gas-liquid mixture and the raw acetylene gas originally in the cathode liquid storage chamber. The other end of the cathode liquid storage chamber is connected to the fourth end of the cathode chamber opposite to the third end. The cathode liquid storage chamber is adapted to input the electrolyte in the cathode liquid storage chamber into the cathode chamber so that the electroreduction of bicarbonate occurs in the cathode chamber to generate CO, thereby generating a second gas-liquid mixture.

[0162] The anode liquid storage chamber, one end of the anode liquid storage chamber is connected to 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 an oxygen evolution reaction occurs in the anode chamber to generate O 2 and H + , thereby generating a first gas-liquid mixture, and a gas dispersion port is provided on the anode liquid storage chamber.

[0163] Wherein, 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 dispersion port of the anode liquid storage chamber.

[0164] The acetylene carbonylation reaction liquid storage chamber, the carbonylation reaction gas inlet of the acetylene carbonylation reaction liquid storage chamber is connected to the cathode liquid storage chamber gas outlet, and the acetylene carbonylation reaction liquid storage chamber is adapted to input CO and C in the mixed gas into the acetylene carbonylation reaction liquid storage chamber 2 H 2 to carry out the acetylene carbonylation reaction to generate the target product dimethyl maleate and other high-carbon ester products, and the unreacted gas is discharged through the gas outlet provided on the acetylene carbonylation reaction liquid storage chamber.

[0165] According to an embodiment of the present invention, the electrocatalytic device further includes: 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.

[0166] According to an embodiment of the present invention, the electrocatalytic device further includes: 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 includes: a gas mass flowmeter, connected to the raw acetylene gas inlet of the cathode liquid storage chamber, for controlling the gas flow rate of the raw acetylene gas and transporting the raw acetylene gas into the cathode liquid storage chamber.

[0168] According to an embodiment of the present invention, the electrocatalytic device further includes: an anode electrode disposed between the anode chamber and the cation exchange membrane and 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 includes: a cathode electrode disposed between the cathode chamber and the cation exchange membrane and 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 a carbon cloth or a carbon felt loaded with any catalyst, and the catalyst includes: nickel, iron, zinc, silver nanoparticles or porous noble 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 liquid storage chamber is acetonitrile, methanol, methanesulfonic acid, palladium bromide, and anhydrous lithium bromide. 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 types of the palladium salt are 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.

[0174] According to an embodiment of the present invention, in the electrocatalytic device, CO in the mixed gas is absorbed and utilized in the cathode chamber 2 , so as to reduce the carbon dioxide emission in the crude acetylene gas; in the thermal catalytic device, the solution in the acetylene carbonylation reaction liquid storage chamber reacts so that carbon monoxide and acetylene undergo an acetylene carbonylation reaction to generate dimethyl maleate, realizing the upgraded utilization of the crude acetylene gas.

[0175] According to an embodiment of the present invention, a two-step cascade device combining electrocatalysis and thermal catalysis is provided, which utilizes the H generated by the anode under voltage drive + and in-situ converts bicarbonate into CO in the cathode chamber of the electrolytic cell 2 , and performs CO 2 electroreduction to generate CO and OH - , and through the electrolyte circulation, CO in the crude acetylene gas is removed in the cathode liquid storage chamber 2Capture and absorption are carried out to generate bicarbonate, thereby supplementing the bicarbonate consumed in the cathode chamber. Acetylene and the generated CO are mixed in the cathode liquid storage chamber and then transported to the acetylene carbonylation reaction liquid storage chamber for the acetylene carbonylation reaction to generate high-carbon esters such as dimethyl maleate, so as to solve the problems of upgrading the utilization of low-value crude acetylene gas and carbon dioxide emission reduction in the acetylene production process.

[0176] See Figure 1 , Figure 1 is a schematic structural diagram 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 gas inlet; 22 - gas mass flowmeter gas 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 (anode liquid storage device liquid outlet pipeline); 52 - the other end of the anode liquid storage chamber (anode liquid storage device liquid inlet pipeline); 6 - cathode liquid storage chamber (cathode liquid storage device); 61 - one end of the cathode liquid storage chamber (cathode liquid storage device liquid outlet pipeline); 62 - the other end of the cathode liquid storage chamber (cathode liquid storage device liquid inlet pipeline); 63 - crude acetylene gas inlet (crude acetylene inlet pipeline); 64 - cathode liquid storage chamber gas outlet (mixed gas outlet); 7 - acetylene carbonylation reaction liquid storage chamber (acetylene carbonylation reaction device); 71 - carbonylation reaction gas inlet (inlet of the acetylene carbonylation reaction device); 72 - carbonylation reaction liquid storage chamber gas outlet (outlet of the acetylene carbonylation reaction device).

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

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

[0179] The electrolytic cell 1 is the main structure of the electrocatalytic device, used for carrying out the electroreduction of bicarbonate to generate CO, and the CO in the crude acetylene gas 2 is removed by the OH generated in the electrolytic cell 1- is captured. Among them, the crude acetylene gas can be the crude acetylene gas actually generated in the industrial production of acetylene or a mixed gas of a certain proportion of C 2 H 2 and CO 2 .

[0180] The acetylene carbonylation reaction liquid storage chamber 7 is the main structure of the thermal catalytic device, which is used to carry out the acetylene carbonylation reaction to generate a series of high-carbon ester products such as dimethyl maleate. The gas for the acetylene carbonylation reaction is the C in the mixed gas output from the cathode liquid storage chamber outlet to the acetylene carbonylation reaction liquid storage chamber 2 H 2 and CO.

[0181] The cation exchange membrane 12 is arranged in the electrolytic cell 1, separating the electrolytic cell 1 into an anode chamber 11 and a cathode chamber 13. The anode chamber 11 undergoes an oxygen evolution reaction (OER) to dissociate water molecules into H + , H + migrates through the cation exchange membrane 12 to the cathode chamber 13. In the cathode chamber 13, bicarbonate first combines with the dissociated H + to generate CO 2 , and then CO 2 is in-situ reduced on the cathode catalyst to form CO. The OH - generated in the cathode chamber 13 can capture CO 2 from the crude acetylene gas, while replenishing the consumed HCO 3 - . Among them, 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 communicated with the liquid inlet 42 of the second peristaltic pump 4, and the liquid outlet 41 of the second peristaltic pump 4 is communicated with the third end 131 of the cathode chamber 13. The cathode liquid storage chamber 6 is provided with a crude acetylene gas inlet 63, and the inlet 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 into 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 - can capture CO 2 in the crude acetylene gas 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, and the second gas-liquid mixture is transported back to the cathode liquid storage chamber 6. The OH - generated in the cathode chamber 13 will capture CO 2, thus, to a certain extent, supplementing the HCO consumed in the cathode chamber 13 3 - . Among them, the gas of the second gas-liquid mixture contains CO, H 2 .

[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 dispersion port is arranged on the anode liquid storage chamber 5, and the gas dispersion 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 in the anode liquid storage chamber into the anode chamber 11. The electrolyte in the anode liquid storage chamber 5 contains the pre-stored electrolyte 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, H 2 and electrolyte.

[0185] According to an embodiment of the present invention, the other end 62 of the cathode liquid storage chamber 6 is communicated with the fourth end 132 of the cathode chamber 13 opposite to the third end 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 further arranged in the cathode liquid storage chamber 6, and the cathode liquid storage chamber gas outlet 64 can be used to output the gas in the second gas-liquid mixture and the original crude acetylene gas in the cathode liquid storage chamber from the cathode liquid storage chamber gas outlet to the acetylene carbonylation reaction liquid storage chamber 7, and CO and C in the output mixed gas 2 H 2 A series of high-carbon ester products such as dimethyl maleate are generated by the acetylene carbonylation reaction in the acetylene carbonylation reaction liquid storage chamber 7.

[0187] It should be understood that Figure 1 The shown is only an example of the structural composition of the embodiment of the present invention to help those skilled in the art understand the technical content of the present invention,[[]]END]] Figure 1 The anode liquid storage chamber 5, the cathode liquid storage chamber 6 and the acetylene carbonylation reaction liquid storage chamber 7 in Figure 1 are shown in the shape of a box, but it does not mean that the components of the present invention are limited to

[0188] Similarly, there are no restrictions on the connection manners of the anode liquid storage chamber 5, the cathode liquid storage chamber 6 to the electrolytic cell 1 and the connection manner of the acetylene carbonylation reaction liquid storage chamber 7 to the cathode liquid storage chamber 6. In some embodiments of the present invention, it can be any connection manner that can play a role in gas-liquid circulation, such as a rigid pipe, a plastic hose, a silica gel tube, a pneumatic joint, etc. According to the embodiments of the present invention, when treating the crude acetylene gas, 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 is mixed with the gas in the second gas-liquid mixture in the cathode liquid storage chamber 6 and jointly output to the acetylene carbonylation reaction liquid storage chamber 7.

[0189] According to the embodiments of the present invention, a voltage is applied to the electrolytic cell 1, and OER occurs in the anode chamber 11 to dissociate water molecules into H + ,H + migrates to the cathode chamber 13 through the cation exchange membrane 12. H 2 O in the electrolyte in the anode chamber 11 undergoes a reaction 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] 2H 2 O - 4e - →4H + +O 2 (I);

[0191] At this time, the gas component in the first gas-liquid mixture only contains O 2 gas. The first gas-liquid mixture flows out through the second end 112 of the anode chamber 11 opposite to the first end and is introduced into the anode liquid storage chamber 5. The gas component in the mixture is discharged through the gas dispersion 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, repeating the above process to realize the circulation of the electrolyte.

[0192] According to the embodiments of the present invention, H 2 O in the anode chamber 11 undergoes OER as shown in formula (I) under the drive of voltage to generate H + ,H + enters the cathode chamber 13 through the cation exchange membrane; the crude acetylene gas will be input into the cathode liquid storage chamber 6 through the crude acetylene gas inlet 63 of the cathode liquid storage chamber 6, the electrolyte in the cathode liquid storage chamber 6 is input into the cathode chamber 13, and HCO 3 - in the electrolyte combines with H + migrated from the anode chamber 11 to in-situ generate CO2 , further CO is generated 2 The electroreduction reaction is as shown in Formula (II) and Formula (III), and OH is generated simultaneously - , 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 CO in the crude acetylene gas in the cathode liquid storage chamber 6 2 will be captured by OH - and react as shown in Formula (IV) to generate HCO 3 - , so that the HCO consumed in the cathode chamber 13 can be supplemented to a certain extent. Here, the OH generated by the electroreduction reaction of bicarbonate in the cathode chamber 13 3 - is used as the medium for capturing CO in the crude acetylene gas. During the power-on process, OH will always dissociate - , so no other capturing medium is needed, avoiding the energy-intensive capturing medium regeneration step during the CO capture process; at this time, the gas components of the second gas-liquid mixture contain H 2 and CO in addition to CO gas, so as to realize the utilization of CO in the crude acetylene gas and solve the problem that it is difficult to directly carry out the electroreduction reaction of CO on the crude acetylene gas - ; and the C 2 in the crude acetylene gas other than CO does not react with the electrolyte. After entering the cathode liquid storage chamber 6 with the second gas-liquid mixture, the gas in the second gas-liquid mixture is mixed with the original crude acetylene gas in the cathode liquid storage chamber and is output from the gas outlet 64 of the cathode liquid storage chamber 6 to the acetylene carbonylation reaction liquid storage chamber 7 for acetylene carbonylation reaction 2 2 2 2 2 2 2

[0193] Further, CO and C in the mixed gas output to the acetylene carbonylation reaction liquid storage chamber 7 2 2 under the action of the carbonylation solution, undergo an acetylene carbonylation reaction to generate dimethyl maleate (C 6 8 4 ), as shown in Formula (V), diethyl maleate (C 8 12 4 ), as shown in Formula (VI), dipropyl maleate (C 10 16 4 ), as shown in Formula (VII), dibutyl maleate (C 12 20 4 ​​​​​​​​​​​​​​​​), such as in formula (VIII), dipentyl maleate (C 14 H 24 O 4 ), as in formula (IX). The relevant reactions are as follows:

[0194] HCO 3 - +H + →CO 2 +H 2 O (II),

[0195] CO 2 +H 2 O + 2e - →CO + H 2 + 2OH - (III),

[0196] CO 2 +OH - →HCO 3 - (IV),

[0197] C 2 H 2 +CO + CH 3 OH → C 6 H 8 O 4 (V),

[0198] C 2 H 2 +CO + CH 3 CH 2 OH → C 8 H 12 O 4 (VI),

[0199] C 2 H 2 +CO + CH 3 CH 2 CH 2 OH → C 10 H 16 O 4 (VII),

[0200] C 2 H 2 +CO + CH 3 CH 2 CH 2 CH 2 OH → C 12 H 20 O 4 (VIII),

[0201] C 2H 2 +CO+CH 3 CH 2 CH 2 CH 2 CH 2 OH→C 14 H 24 O 4 (IX).

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

[0203] The O 2 generated by OER occurring in the anode chamber 11 of the present invention is mixed with the electrolyte in the anode chamber 11 to form a first gas-liquid mixture. The first gas-liquid mixture flows back into the anode liquid storage chamber 5 through the communication 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. The gas in the first gas-liquid mixture is discharged through the gas dispersion 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] Combined Figure 1 As shown, the first peristaltic pump 3 is disposed between the anode liquid storage chamber 5 and the anode chamber 11. The liquid inlet 31 of the first peristaltic pump 3 is communicated with one end 51 of the anode liquid storage chamber 5, and the liquid outlet 32 of the first peristaltic pump 3 is communicated with 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 the first peristaltic pump 3 from one end 51 of the anode liquid storage chamber 5. 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] As Figure 1As 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 1 As 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 embodiments of the present invention, a mass flowmeter is used to adjust the flow rate of the mixed gas. It should be understood that there is no limitation on the gas flow rate control device, and according to actual needs, it can be replaced by any device that can control the gas flow rate, such as a rotameter, 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 and electrically connected to the anode of the electrochemical workstation.

[0216] Combined with Figure 1 As shown, the anode electrode 14 is disposed on one side of the cation exchange membrane 12 and 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. Among them, the selection of the anode electrode material determines the overpotential reaction of oxygen evolution at the anode.

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

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

[0219] It should be understood that the above selection of the anode electrode material is only an example, and according to actual needs, it can be replaced by one or more of materials such as platinum metal and aluminum metal, and its shape has no specific requirements.

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

[0221] Combined with 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 an embodiment of the present invention, the selection of the cathode electrode material is an important factor determining the electroreduction effect of the generated bicarbonate and is also a key factor determining the concentration of the high-carbon ester generated in 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 to catalyze CO 2 and H 2 O in the cathode chamber 13 to generate CO and H 2 .

[0223] In some embodiments of the present invention, the cathode electrode material can be any catalyst-loaded carbon cloth or carbon felt, and the catalyst can include: nickel, iron, zinc, silver nanoparticles or porous noble metals. By controlling the type of catalyst, a mixture of CO and H with different ratios can also be obtained. 2 mixture gas.

[0224] It should be understood that the selection of the above cathode electrode material is only an example. According to actual needs, those skilled in the art can 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 ratio in the acetylene carbonylation reaction liquid storage chamber is acetonitrile, alcohol, methanesulfonic acid, palladium bromide, anhydrous lithium bromide.

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

[0228] In addition, the present invention places no restrictions on the selection of bicarbonate. In the embodiments of the present invention, the electrolyte can be a saturated potassium bicarbonate solution. According to actual needs, a saturated sodium bicarbonate solution or the like (only an example) can also be selected, and any electrolyte that can meet the electrochemical requirements.

[0229] According to an embodiment of the present invention, in the electrocatalytic device, CO in the crude acetylene gas is utilized in the cathode chamber 2 , so as 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 liquid storage chamber react in the carbonylation solution to generate high-carbon ester products such as dimethyl maleate, realizing the upgrading and 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 can be the liquid inlet of the anode chamber, and the second end 112 of the anode chamber 11 can be the liquid outlet of the anode chamber. The third end 131 of the cathode chamber 13 can be the liquid inlet of the cathode chamber, and the fourth end 132 of the cathode chamber 13 can be the liquid outlet of the cathode chamber.

[0231] According to an embodiment of the invention, one end 61 of the cathode liquid storage chamber 6 can be the liquid outlet of the cathode liquid storage chamber, and the other end 62 of the cathode liquid storage chamber 6 can be the liquid inlet of the cathode liquid storage chamber. The crude acetylene gas inlet 63 on the cathode liquid storage chamber 6 serves as the crude acetylene gas inlet output from the mass flowmeter, and the cathode liquid storage chamber gas outlet 64 on the cathode liquid storage chamber 6 is arranged 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 can be the liquid outlet of the anode liquid storage chamber, and the other end 52 of the anode liquid storage chamber 5 can be the liquid inlet of the anode liquid storage chamber. The gas diffusing ports of the anode liquid storage chamber are evenly distributed on the cover of the anode liquid storage chamber 5.

[0233] Combined with Figure 1 As shown, a simple description is given of the electrolyte circulation of this electrocatalytic device and the process of upgrading and utilizing the crude acetylene gas.

[0234] As Figure 1 As shown, this electrocatalytic device can include: an electrolytic cell 1, a gas mass flowmeter 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. A cation exchange membrane 12 is arranged in the electrolytic cell 1 for transporting H + generated by the oxygen evolution reaction (OER) in the anode chamber, and at the same time separating the electrolytic cell 1 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 liquid storage chamber 6. The first peristaltic pump 3 is arranged between the anode liquid storage chamber 5 and the anode chamber 11 for pumping the electrolyte in the anode liquid storage chamber 5 into the anode chamber 11. The second peristaltic pump 4 is arranged between the cathode liquid storage chamber 6 and the cathode chamber 13 for pumping the electrolyte absorbed with CO 2 in the cathode liquid storage chamber 6 into the cathode chamber 13. The anode liquid storage chamber 5 and the cathode liquid storage chamber 6 are respectively used for storing and circulating the electrolyte.

[0236] During the treatment process of 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 inside the electrolytic cell 1. In the anode chamber 11 of the electrolytic cell 1, OER occurs to generate H + and O 2 , and H +Diffuse into the cathode chamber 13. The gas mass flowmeter 2 controls the flow rate of the crude acetylene gas. The inlet 21 of the gas mass flowmeter is connected to the steel cylinder storing the crude acetylene gas, and the 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 introduced into the cathode liquid storage chamber 6 through the inlet and outlet of the gas mass flowmeter 2 and the crude acetylene gas inlet 63 provided on the cathode liquid storage chamber 6. The second peristaltic pump 4 pumps the electrolyte in the cathode liquid storage chamber 6 from one end 61 (liquid outlet) of the cathode liquid storage chamber 6 through the liquid inlet 42 and the liquid outlet 41 of the second peristaltic pump 4 into the cathode chamber 13. The electrolyte reacts in the cathode chamber 13 (i.e., the above reaction formulas II and III), generating CO 2 , CO and H 2 mixed gas, forming a second gas-liquid mixture with the electrolyte. Among them, CO 2 in the crude acetylene gas in the cathode liquid storage chamber 6 is absorbed and converted into bicarbonate and enters the electrolyte, realizing the separation and utilization of CO 2 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 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 as to output the gas in the second gas-liquid mixture and the original crude acetylene gas in the cathode liquid storage chamber to the acetylene carbonylation reaction liquid storage chamber 7. CO and C 2 H 2 in the mixed gas can undergo an acetylene carbonylation reaction in the acetylene carbonylation reaction liquid storage chamber 7 to generate a series of high-carbon ester products such as the target product dimethyl maleate. 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 6, 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 an applied voltage and a cathode catalyst, the solution in the cathode chamber undergoes a reaction (i.e., the above reaction formulas II and III), generating a mixed gas with a certain proportion of CO, CO 2 and H 2 , completing the conversion of CO 2 . At the same time, by controlling the magnitude of the applied voltage and the type of the cathode material catalyst, the concentration of the generated CO can be regulated.

[0238] OER occurs in the anode chamber 11 to generate O 2, it is mixed with the electrolyte in the anode chamber 11 to form a first gas-liquid mixture. The first gas-liquid mixture flows back into the anode storage chamber 5 through the connection between the second end 112 (the liquid outlet of the anode chamber) of the anode chamber and the other end 52 (the liquid inlet) of the anode storage chamber 5, and is discharged through the gas dispersion port in the anode storage chamber 5. The electrolyte from which the gas is separated is recycled to provide H + .

[0239] According to the embodiments of the present invention, the and H generated by the anode under voltage drive can be utilized + , and the bicarbonate is in-situ converted into CO in the cathode chamber of the electrolytic cell 2 , for CO 2 electroreduction to generate CO and OH - , and the CO in the crude acetylene gas is captured and absorbed through the electrolyte circulation in the cathode storage chamber 2 to form bicarbonate, thereby supplementing 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 an acetylene carbonylation reaction to generate a series of ester products such as dimethyl maleate, so as to solve the problems of upgrading the utilization of low-value crude acetylene gas and carbon dioxide emission reduction in the acetylene production process.

[0240] According to the embodiments of the present invention, adjacent components of the electrocatalytic device can be pressed by silica gel gaskets and external nuts to play a sealing role and ensure 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 combining electrocatalysis and thermal catalysis to produce high-carbon ester compounds from crude acetylene. The present invention provides a two-step cascade system that combines 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 is beneficial to 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 and H generated by the anode under voltage drive + , and the bicarbonate is in-situ converted into CO in the cathode chamber of the electrolytic cell 2 , for CO 2 electroreduction to generate CO and OH - , and the CO in the crude acetylene gas is captured and absorbed through the electrolyte circulation in the cathode storage chamber 2 to form bicarbonate, thereby supplementing 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 an acetylene carbonylation reaction to generate high-carbon esters such as dimethyl maleate, so as to solve the problems of upgrading the utilization of low-value crude acetylene gas and carbon dioxide emission reduction in the acetylene production process.

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

[0244] Example 1

[0245] This example provides a two-step cascade device for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermal catalysis, as well as a corresponding method for preparing high-carbon ester compounds from crude acetylene by electrocatalysis and thermal catalysis. The structure of the reaction device is as Figure 1 shown.

[0246] Specific steps: Connect an electrochemical workstation to the electrocatalysis device part, apply a constant current of 100 mA cm -2 , set the peristaltic pump flow rate to 20 sccm, set the gas mass flowmeter flow rate to 10 sccm, and the ratio of crude acetylene gas is C 2 H 2 :CO 2 is 9:1. Connect the reacted gas to the thermal catalysis reaction tank. In the thermal catalysis tank, the solution ratio in the acetylene carbonylation reaction bottle is 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. Set the rotor speed of the magnetic stirrer to 400 rpm and react at 25 °C for 1 hour, and then collect the product.

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

[0248] The above has introduced in detail a two-step cascade device and method for preparing high-carbon ester compounds from crude acetylene by combining electrocatalysis and thermocatalysis. In this article, specific examples are used to elaborate on the principle and implementation mode of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of this invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within 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; 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); 2) introducing crude acetylene gas into the gas-liquid mixture obtained in the above step, absorbing CO2 in the crude acetylene gas, thereby obtaining a mixed gas containing C2H2 and CO, and then introducing the mixed gas into an acetylene carbonylation solution, wherein C2H2 and CO are catalyzed to undergo acetylene carbonylation reaction, thereby obtaining a high carbon ester compound; The acetylene carbonylation solution comprises acetonitrile, an alcohol solvent, methanesulfonic acid, a palladium salt and anhydrous lithium salt; The high carbon ester compound is one or more of dimethyl butenedioate, diethyl butenedioate, dipropyl butenedioate, dibutyl butenedioate and dipentyl butenedioate; The two-step cascade device used in the method comprises: 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.

2. The method according to claim 1, characterized in that 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.

3. The method according to claim 1, 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).

4. The method according to claim 1, characterized in that: 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. The method according to claim 1, 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.

6. The method according to claim 1, characterized in that 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 method according to claim 1, 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 method according to claim 1, 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 method according to claim 1, 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 method according to claim 1, 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 dilute sulfuric acid solution; The acetylene carbonylation reaction device is provided with an acetylene carbonylation solution.

Images