A device and method for producing hydrogen and sulfur by utilizing industrial organic solid waste

Abstract

The present invention discloses a device and method for producing hydrogen and co-producing sulfur using industrial organic solid waste, specifically relating to the technical field of industrial solid waste treatment. The device includes a pyrolysis gas synthesis tower, a plasma tower, a gas-liquid separator, and an electrolysis device; wherein, the electrolysis device includes a cathode electrode, a diaphragm, and an anode electrode; the gas pyrolyzed by the pyrolysis gas synthesis tower enters the plasma tower for reaction, converting gaseous pollutants such as H2S and NH3 into useful hydrogen and solid sulfur for recovery. The gas enters the gas-liquid separator, and the mixed gas containing hydrogen is separated and then undergoes subsequent treatment; the liquid enters the anode electrode of the electrolysis device, and after electrolysis, H2 is generated from the HCl therein, and pure hydrogen is collected by the cathode electrode. The present invention can enable both efficient and rapid electron conduction and proton transfer, and at the same time avoid HCl from only entering the wastewater treatment system as waste, realizing a new process of directly converting the difficult-to-solve heteroatom Cl in garbage into NaClO.

Description

Technical Field

[0001] The invention relates to the technical field of industrial solid waste treatment, and in particular to a device and method for producing hydrogen and co-producing sulfur by utilizing industrial organic solid waste. Background Art

[0002] At present, the amount of industrial and urban organic solid waste is increasing, including the residual organic waste that is difficult to decompose from the excavation of the previous landfill site. Usually, this type of waste also contains heteroatom pollution factors such as S, N, and Cl, which makes it more difficult to deal with. Although the incineration method can greatly reduce the amount of solid waste, incineration usually produces a large amount of dioxins and fly ash, sulfur dioxide, and nitrogen oxides, causing serious secondary pollution. In particular, fly ash still needs to be landfilled in a new site and its treatment cost increases by more than ten times. The method of using a new site for landfill may also become a new point source of pollution, which will have a long-term impact on the local environment.

[0003] Green hydrogen is generated by using renewable energy (such as solar energy, wind energy, nuclear energy, etc.) to generate electricity, which is then converted into hydrogen energy through water electrolysis hydrogen production equipment. Because it only requires water in the production process, carbon emissions can reach net zero.

[0004] Chinese patent CN116492953A, a full-process photocatalytic decomposition of organic solid waste and co-production of green hydrogen cyclic reaction device and method, the method includes placing untreated organic solid waste in a material delivery platform, and at the same time ensuring that the pretreatment reactor is an acidic or alkaline environment required for the pretreatment reaction, and after the heating device is heated to the specified temperature, the material platform is uniformly lowered into the pretreatment reactor using the glass fiber rope of the driving device, and the material is preliminarily decomposed at the set temperature. After the material is dissolved, the valve is opened to put the obtained solution into the decomposition liquid temporary storage bottle, and then the three-way valve is opened, and the pump starts to work, and the solution obtained in the first step is sucked in a nitrogen atmosphere. After inhalation, the three-way valve and the pump are used to perform a cyclic photocatalytic flow reaction, and the liquid product obtained and the gas product with hydrogen as the main component are collected by the final product collection bottle. However, this method only uses organic solid waste to produce hydrogen, but does not further treat heteroatoms such as S, N, and Cl in the solid waste, which leads to incomplete solid waste treatment. In addition, the photocatalytic yield and output are very low.

[0005] Chinese patent CN115108546A, a system and method for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers, the system includes: a melt feeding device, a pyrolysis device, a vapor deposition device, a pyrolysis gas purification and utilization device, a gas device, a carbon product collection device and a catalyst regeneration device. The method includes heating and melting the waste plastic into the pyrolysis device, passing the generated pyrolysis gas into the vapor deposition device, separating the hydrogen from the residual gas after the reaction and storing it; the conveyor belt substrate circulates in the device, cools after the vapor deposition reaction, recovers the carbon product, reloads and dries the catalyst, and then circulates for the next reaction. Similarly, this patent only converts organic matter into carbon materials and produces hydrogen at the same time, but how to deal with other heteroatoms and how to improve the purity of hydrogen are still difficult problems that need to be solved.

[0006] The electrochemical reduction method has the advantage of high product purity comparable to the biological transformation method, and also has the advantages of fast reaction, high efficiency, safety and reliability compared to the catalytic synthesis method. Its biggest advantage is that it can realize unit operation and simple equipment; however, the electrochemical method requires proton transfer in an electrolyte solution, which greatly limits its use in the electrolysis process of gaseous pollutants. Gaseous HCl should first be dissolved in a liquid solution before effective electrolysis to produce hydrogen, and it needs to be carried out in an electrolytic cell. The traditional electrolytic cell has a large electrode spacing and a large internal resistance, and it needs to increase additional voltage to achieve the purpose of intermolecular dissociation. It has high energy consumption and high cost. Since the electrodes are all metal conductive electrodes, the dense electrodes hinder the transfer of protons, which makes its reaction rate low, the effect poor, and the yield low.

[0007] Therefore, how to reduce the amount of industrial organic solid waste and how to improve the organic solid waste, especially the recycling and treatment process, to reduce its pollution to the environment when disposed of by landfill, incineration, etc., remain important challenges today. Summary of the invention

[0008] To this end, the present invention provides a device and method for producing hydrogen and sulfur in combination using industrial organic solid waste to solve the above-mentioned problems.

[0009] In response to these defects, the present invention integrates the diaphragm and the electrode into an innovative electrolysis system, integrating the anode electrode, ion selective diaphragm, and cathode electrode into a whole, with no gaps between the anode-diaphragm-cathode, so that the electron conduction resistance (internal resistance) and the proton transfer resistance are minimized. At the same time, the anode electrode, cathode electrode, and diaphragm are all made of porous material structures, which greatly shortens the transfer distance of protons / ions, and realizes multi-dimensional, multi-channel, barrier-free transfer of protons / ions to achieve the maximum reaction rate.

[0010] Thermal cracking and gasification of organic solid waste under anaerobic conditions can convert heteroatom compounds containing S, N, Cl, etc. into their hydrides, such as: H2 S. NH 3 , HCl and other gaseous substances, and then use appropriate processes to convert H 2 S. NH 3 Extracting hydrogen from gaseous substances such as HCl in the form of hydrogen can not only reduce pollution properties, but also recycle it as industrial raw materials, such as:

[0011] H 2 S → H 2 + S, H 2 S can be recovered as hydrogen and sulfur;

[0012] NH 3 → H 2 + N 2 , NH 3 Can be recovered as hydrogen and discharged as harmless nitrogen;

[0013] HCl → H 2 + Cl 2 HCl can be used to recover hydrogen and chlorine. Chlorine is usually recovered in the form of NaClO, but it can also be recovered in the form of ClO 2 Recycle.

[0014] The present invention aims at the technical inadequacies and serious defects of the current methods for treating such pollutants, and adopts plasma technology to remove NH 3 and H 2 S captures hydrogen (H 2 ) and recover sulfur (S 2 ). Hydrogen (H) is extracted and recovered from HCl by electrolysis. 2 ) and recover NaClO.

[0015] Plasma technology using water as the atomic source effectively converts H 2 The hydrogen in S is hydrogen gas (H 2 ) is extracted, and the remaining S is extracted from the gaseous H 2 S is separated and recovered.

[0016] In order to achieve the above object, the present invention provides the following technical solutions:

[0017] According to one aspect of the present invention, a device for producing hydrogen and sulfur in combination using industrial organic solid waste is provided, the device comprising a cracking gas synthesis tower, a plasma tower, a gas-liquid separator and an electrolysis device;

[0018] Wherein, the electrolysis device comprises a cathode electrode, a diaphragm and an anode electrode;

[0019] The cracked gas from the cracking gas synthesis tower enters the plasma tower for reaction. The tower is equipped with positive and negative electrodes to generate plasma atmosphere under the action of electric field. High-energy plasma such as hydroxyl radicals are generated between the electrodes. A porous medium (the medium matrix material is foam ceramic or sponge glass) is provided between the positive and negative electrodes, and a catalyst is attached to it to form an electrode body. Multiple electrode bodies are arranged in a honeycomb shape. 2 S. NH 3 The gaseous substances dissociate into H 2 、N 2 , S. Among them, S is recovered as solid sulfur, and the gas enters the gas-liquid separator to separate the mixed gas with hydrogen for subsequent treatment;

[0020] The solution containing HCl dissolved in the liquid enters the anode electrode of the electrolysis device, and after electrolysis, HCl produces H 2 , pure hydrogen is collected by the cathode electrode.

[0021] Furthermore, the cathode electrode material is selected from sponge lead; lead is plated on foam ceramics or mesoporous foam glass to prepare porous sponge lead; electrocatalyst is filled on foam ceramics or mesoporous foam glass; and electrocatalyst is filled on foam nickel with foam nickel as a conductive skeleton; wherein the electrocatalyst is NiO, CuO, MgO, Re 2 O 3 , PbO 2 A mixture of at least two components.

[0022] The method of filling the electrocatalyst is chemical plating and / or electroplating.

[0023] Furthermore, one side of the cathode electrode is chemically plated with an electrocatalyst mixture; wherein the electrocatalyst is NiO, CuO, MgO, Re 2 O 3 , PbO 2 A mixture of at least two components.

[0024] The types of electrocatalysts mentioned in the two parts of the present invention are the same. In the same embodiment, the part requiring the electrocatalyst is a completely consistent material mixture.

[0025] Furthermore, the membrane material includes an ion selective exchange resin membrane and a natural fibrous silicate mineral.

[0026] Furthermore, the natural fibrous silicate mineral is one or more of serpentine, hornblende, actinolite, anthophyllite, amosite and tremolite.

[0027] Furthermore, the diaphragm material is tightly attached to the side of the cathode electrode without electrocatalyst under a certain pressure without leaving any gaps; the thickness of the diaphragm is 0.2 to 5.0 mm.

[0028] Furthermore, the anode electrode is formed on the other side of the diaphragm by chemical plating with Pb(NO 3 ) 2 The conductive coating of the precursor is then electroplated with MnO 2 A mixed solution consisting of CuO, graphite and carbon black is prepared to obtain an anode electrode layer.

[0029] Furthermore, the device also includes a first pressure swing adsorption, which is used to remove the by-product carbon dioxide in the gas separated by the gas-liquid separator. The by-product carbon dioxide is mixed with oxygen and enters the cracking gasification synthesis tower for further reaction. The mixed gas from which carbon dioxide is removed is subjected to a second pressure swing adsorption to obtain pure hydrogen. The gas removed by the second pressure swing adsorption is returned to the mixed gas for pressure swing adsorption treatment again.

[0030] Furthermore, the chlorine gas produced in the electrolysis device is introduced into an alkaline solution to obtain NaClO as a by-product.

[0031] According to another aspect of the present invention, a method for producing hydrogen and co-producing sulfur using industrial organic solid waste is provided, the method comprising:

[0032] Step 1: Preparation of electrolysis device

[0033] Select the cathode electrode material and chemically plate NiO, CuO, MgO, Re on one side of the material. 2 O 3 , PbO 2 A mixture of at least two of the above to obtain a highly active electrocatalytic cathode electrode layer;

[0034] Apply a certain pressure to press the diaphragm material on one side of the highly active electrocatalytic cathode electrode layer, so that the diaphragm and the cathode electrode layer fit tightly together without leaving any gaps;

[0035] Plating an anode electrode layer on the other side of the diaphragm;

[0036] The cathode electrode layer, the diaphragm layer, and the anode electrode layer are baked and aged at 150°C to 200°C to form an integrated electrode system with a porous structure;

[0037] Step 2: Treatment of industrial waste

[0038] The cracked gas from the cracking gas synthesis tower enters the plasma tower for reaction, solid sulfur is recovered, and the gas enters the gas-liquid separator to separate the mixed gas with hydrogen for subsequent treatment;

[0039] The liquid enters the anode electrode of the electrolysis device, and after electrolysis, pure hydrogen is collected by the cathode electrode.

[0040] Furthermore, in the step 1, the cathode electrode material is selected as sponge lead; lead is plated on foam ceramic or mesoporous foam glass to prepare porous sponge lead; electrocatalyst is filled on foam ceramic or mesoporous foam glass; and one of the electrocatalysts is filled on the foam nickel with foam nickel as the conductive skeleton; wherein the electrocatalyst is NiO, CuO, MgO, Re 2 O 3 , PbO 2 A mixture of at least two components.

[0041] Furthermore, in the step 1, the membrane material includes an ion selective exchange resin membrane and a natural fibrous silicate mineral.

[0042] Furthermore, in the step 1, the anode electrode layer is plated with Pb(NO 3 ) 2 The conductive coating of the precursor is then electroplated with MnO 2 A mixed solution consisting of CuO, graphite and carbon black is prepared to obtain an anode electrode layer.

[0043] Furthermore, the manufactured anode electrode, ion selective membrane, and cathode electrode are integrated into an integrated electrode, and the conductivity between the electrodes and the insulation between the membranes are checked and tested.

[0044] The present invention has the following advantages:

[0045] In the present invention, the gas cracked by the cracking gas synthesis tower enters the plasma tower for reaction, and the H 2 S. NH 3 Gaseous pollutants such as 2 and S, hydrogen and solid sulfur are recovered; the present invention uses an electrochemical method to efficiently convert hydrogen in HCl into hydrogen (H 2 ), so that hydrogen can be further recovered, extracted and reused. The present invention is a bold innovation in the electrolysis device, integrating the anode electrode, electrolyte membrane (diaphragm), and cathode electrode together, and using porous electrodes to construct a multi-dimensional super strong channel for protons. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0047] The structures, proportions, sizes, etc. illustrated in this specification are only used to match the contents disclosed in the specification so as to facilitate understanding and reading by persons familiar with the technology. They are not used to limit the conditions under which the present invention can be implemented, and therefore have no substantial technical significance. Any structural modification, change in proportion or adjustment of size shall still fall within the scope of the technical contents disclosed in the present invention without affecting the effects and purposes that can be achieved by the present invention.

[0048] Figure 1 The electrolysis principle diagram provided by the present invention;

[0049] Figure 2 A device for producing hydrogen and sulfur from industrial organic solid waste provided in Example 1 of the present invention;

[0050] Figure 3 A diagram of the internal ionization device of the plasma tower provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0051] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0052] The principle of electrolysis Figure 1 As shown:

[0053] After the DC power supply is turned on, HCl dissociates into H in the anode electrode (anode chamber). + and Cl - , where H + Migrate to the cathode electrode (cathode chamber), gain electrons, generate hydrogen, and Cl in the anode chamber loses electrons to generate chlorine. The specific reaction is as follows:

[0054] Cathode chamber:

[0055] H + + e - → H 2 ;

[0056] Anode chamber:

[0057] Cl - -e - →Cl 2 ;

[0058] HCl→Cl - + H + .

[0059] Side reaction: Water undergoes ionization reaction using the same principle:

[0060] Anode chamber:

[0061] H 2 O→O 2- +H + ;

[0062] O 2- + e - →O 2 ;

[0063] Cathode chamber:

[0064] H + + e - →H 2 .

[0065] Example 1

[0066] This embodiment provides a device for producing hydrogen and sulfur by using industrial organic solid waste, such as Figure 2 As shown:

[0067] The device comprises: a cracking gasification synthesis tower, a crude synthesis gas storage tank, a plasma tower, a sulfur recovery device, a gas-liquid separator, a first pressure swing adsorption, a mixed gas storage, a second pressure swing adsorption and an electrolysis device;

[0068] The electrolysis device includes a cathode electrode, a diaphragm and an anode electrode.

[0069] The cracked gas from the cracking gas synthesis tower enters the plasma tower (such as Figure 3 As shown, the plasma tower is composed of a positive electrode-porous medium-negative electrode, and the positive electrode-porous medium-negative electrode is coaxially arranged; wherein the negative electrode is composed of a metal mesh structure, the mesh structure material is a mesh metal material, the positive electrode is a tubular structure, and its tube wall is drilled with small holes arranged in an array to form a nozzle, and water vapor is sprayed from the nozzle and evenly distributed between the positive electrode and the negative electrode; the porous medium material is selected from insulating macroporous ceramics, macroporous foamed glass, or heat-resistant fiber / glass fiber) for reaction, solid sulfur is recovered, and the gas enters the gas-liquid separator, and the mixed gas with hydrogen is separated and the carbon dioxide by-product is separated by the first pressure swing adsorption, and the carbon dioxide by-product enters the cracking gasification synthesis tower and is compounded with oxygen for cracking; the mixed gas from which carbon dioxide is separated enters the second pressure swing adsorption after the mixed gas storage to obtain pure hydrogen, and the gas of the second pressure swing adsorption enters the mixed gas storage again. The mixed gas portion after the second pressure swing adsorption separation of hydrogen can be returned to the cracking gasification synthesis tower to further generate hydrogen, and can also be used for unit operations that require heat supply, such as preheating and dehydrating raw materials with the help of a burner;

[0070] The liquid separated by the gas-liquid separator enters the anode electrode of the electrolysis device. After electrolysis, pure hydrogen is collected by the cathode electrode, and the chlorine obtained at the anode further reacts with the alkaline solution to obtain NaClO. The by-product oxygen and by-product carbon dioxide are mixed to form the gas used for cracking in the cracking gasification synthesis tower. The presence of carbon dioxide is conducive to the direct reforming of carbon to produce hydrogen, accelerating the reaction process and reducing the occurrence of carbon deposition.

[0071] Example 2

[0072] This embodiment provides a method for producing hydrogen and sulfur from industrial organic solid waste using the device of embodiment 1.

[0073] Step 1: Preparation of electrolysis device

[0074] The cathode electrode material is selected by plating lead on foam ceramic or mesoporous foam glass to prepare porous sponge lead, and NiO, CuO, PbO are plated on one side of the cathode electrode material. 2 The cathode electrode layer is obtained by mixing components of the mixture; the other side (non-plated side) of the cathode electrode layer is pressed under a pressure of 0.1 MPa with a mixture of an ion selective exchange resin membrane and a natural fibrous silicate mineral (the membrane fibers are tightly fitted without leaving gaps), wherein the natural fibrous silicate mineral is selected from serpentine and hornblende; a diaphragm layer is formed, and the thickness of the diaphragm layer is 0.2 mm.

[0075] On the other side of the diaphragm, Pb(NO 3 ) 2 The conductive coating of the precursor is then electroplated with MnO 2 A mixed solution consisting of CuO, graphite and carbon black forms an anode electrode layer.

[0076] The basic integrated electrode including the cathode electrode layer, the diaphragm layer and the anode electrode layer is baked and aged at 150° C.-200° C. to form an integrated electrode system with a porous structure.

[0077] Step 2: Electrode and electrocatalytic performance testing

[0078] The reactor obtained in step 1 has an integrated electrode with a highly porous anode electrode, a microporous selective ion diaphragm, and a porous or mesoporous cathode electrode, and the anode-diaphragm-cathode are formed into a coaxial structure, ensuring that the electrode structure is firm, safe and reliable, has a long service life, and maintains a high degree of sealing, and has no leakage of hydrogen or chlorine;

[0079] The integrated electrode obtained in step 1 was placed in saturated saline and a voltage of 1.5 V was applied to activate the electrode for 24 hours. Electrode activation mainly depends on the activation of electrochemical catalysts. 2The mixed components of NiO, PbO 2 Converted into Ni and Pb active sites, the final electrode has good conductivity and hydrogen folding performance;

[0080] Electrode activation also increases the MnO 2 , CuO, graphite, carbon black and other high oxygen evolution mixed catalytic activity. After activation, the integrated electrode was tested in 1M sodium chloride solution and the current efficiency was calculated: the current efficiency was 95% ~ 120%, which was qualified.

[0081] Step 3: Plasma hydrogen production and sulfur recovery

[0082] The positive electrode of the plasma power source is connected to a stainless steel wire or tube, and the negative electrode is connected to a mesh metal net to form a wire-cylinder coaxial corona discharge plasma chamber. The stainless steel wire or tube is covered with a quartz glass tube or ceramic tube to prevent the occurrence of large current short circuit and maintain the corona discharge current at the milliampere level. A porous medium is arranged between the positive and negative electrodes. The matrix material of the medium is a macroporous ceramic with good insulation, macroporous foamed glass, or heat-resistant fiber / glass fiber. The porous medium and the metal net are both impregnated with NiO, CeO 2 The catalytic layer, with a Ce / Ni ratio between 5% and 20%, is coated by dip coating and baked at 150°C.

[0083] The temperature of the corona discharge plasma chamber is maintained at 150℃ ~ 200℃ and the pressure is 0.1MPa under the active test conditions. An appropriate amount of water vapor is added to the corona discharge plasma chamber to maintain the atomic source of the corona discharge plasma. The following H 2 S and NH 3 Dissociation:

[0084] H 2 S → H 2 + S;

[0085] NH 3 → H 2 + N 2 ;

[0086] Sulfur is collected at the bottom of the corona discharge plasma chamber and recovered as solid sulfur after cooling and weighing. 3 , H 2 Hydrogen, nitrogen and other mixed gases produced by S decomposition.

[0087] The hydrogen, nitrogen and other mixed gases at the outlet of the corona discharge plasma chamber contain 6% to 8% water vapor and a certain amount of HCl. The mixed gas enters the gas-liquid separator, the water vapor condenses and absorbs HCl, and enters the electrolysis device together to produce hydrogen.

[0088] Step 4: Treatment of industrial waste

[0089] The cracked gas from the cracking gas synthesis tower (oxygen content is not higher than 10%) enters the plasma tower through the crude synthesis gas storage tank for reaction, solid sulfur is recovered, and the gas enters the gas-liquid separator to separate the mixed gas with hydrogen, which is separated into carbon dioxide by-product through the first pressure swing adsorption. The carbon dioxide by-product enters the cracking gasification synthesis tower and is combined with oxygen for cracking; the mixed gas from which carbon dioxide is separated enters the second pressure swing adsorption after mixed gas storage to obtain pure hydrogen, and the gas from the second pressure swing adsorption enters the mixed gas storage again;

[0090] The liquid separated by the gas-liquid separator (the concentration in the HCl absorption liquid is about 3.5%) enters the anode electrode of the electrolysis device. After electrolysis, the pure hydrogen is collected by the cathode electrode, and the chlorine obtained at the anode further reacts with the alkaline solution to obtain NaClO. The by-product oxygen and by-product carbon dioxide are mixed to form the gas used for cracking in the cracking gasification synthesis tower.

[0091] H 2 The conversion rate is as high as 95.0% and Cl 2 The selectivity is as high as 93.0%.

[0092] Example 3

[0093] The difference between this embodiment and embodiment 2 is that:

[0094] The cathode material is nickel foam as the conductive skeleton and the electrocatalyst is filled on the nickel foam (specifically: NiO, CuO, MgO, Re 2 O 3 , PbO 2 The mixed components are filled in the nickel foam, and Ni or Pb is partially reduced under strong current to make it a catalytic electrode with good conductivity and electrocatalytic activity): NiO, CuO, MgO, Re are plated on one side of the cathode electrode material 2 O 3 , PbO 2 The cathode electrode layer is obtained by mixing the components of the cathode electrode layer; the other side (non-plated side) of the cathode electrode layer is pressed under a pressure of 1 MPa with a mixture of an ion selective exchange resin membrane and a natural fibrous silicate mineral (the membrane fibers are tightly fitted without leaving gaps), wherein the natural fibrous silicate mineral is serpentine; a diaphragm layer is formed, and the thickness of the diaphragm layer is 3 mm;

[0095] Step 2: Apply a voltage of 2.0 V to activate the electrode for 10 hours;

[0096] The rest is exactly the same as in Example 2.

[0097] H 2 The conversion rate is as high as 98% and Cl2 The selectivity is as high as 95%.

[0098] Example 4

[0099] The difference between this embodiment and embodiment 2 is that:

[0100] The cathode material is sponge lead, and one side of the cathode electrode material is plated with NiO, CuO, MgO, Re 2 O 3 , PbO 2 The cathode electrode layer is obtained by mixing the components of the cathode electrode layer; the other side (non-plated side) of the cathode electrode layer is pressed under a pressure of 2.0 MPa with a mixture of an ion selective exchange resin membrane and a natural fibrous silicate mineral (the membrane fibers are tightly attached without leaving gaps), wherein the natural fibrous silicate mineral is serpentine; a diaphragm layer is formed, and the thickness of the diaphragm layer is 5 mm;

[0101] Step 2: Apply a voltage of 1.5 V to activate the electrode for 20 hours;

[0102] The rest is exactly the same as in Example 2.

[0103] H 2 The conversion rate is as high as 90% and Cl 2 The selectivity is as high as 99%.

[0104] Example 5

[0105] The difference between this embodiment and embodiment 2 is that:

[0106] The cathode material is made of foam ceramics. The electrocatalyst is filled on the foam glass (specifically: NiO, CuO, Re 2 O 3 , PbO 2 The mixed components are filled in the foam ceramic foam glass, and Ni or Pb is partially reduced under strong current to make it a catalytic electrode with good conductivity and electrocatalytic activity): NiO, CuO, Re are plated on one side of the cathode electrode material 2 O 3 , PbO 2 The cathode electrode layer is obtained by mixing the components of the cathode electrode layer; the other side (non-plated side) of the cathode electrode layer is pressed under a pressure of 2.0 MPa with a mixture of an ion selective exchange resin membrane and a natural fibrous silicate mineral (the membrane fibers are tightly fitted without leaving gaps), wherein the natural fibrous silicate mineral is serpentine; a diaphragm layer is formed, and the thickness of the diaphragm layer is 3 mm;

[0107] Step 2: Apply a voltage of 2.0 V to activate the electrode for 10 hours;

[0108] The rest is exactly the same as in Example 2.

[0109] H 2 The conversion rate is as high as 99% and Cl 2 The selectivity is as high as 90%.

[0110] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A device for producing hydrogen and sulfur from industrial organic solid waste, characterized in that: The device comprises a cracking gas synthesis tower, a plasma tower, a gas-liquid separator and an electrolysis device; Wherein, the electrolysis device comprises a cathode electrode, a diaphragm and an anode electrode; The cracked gas from the cracking gas synthesis tower enters the plasma tower for reaction, solid sulfur is recovered, and the gas enters the gas-liquid separator to separate the mixed gas with hydrogen for subsequent treatment; The liquid enters the anode electrode of the electrolysis device, and after electrolysis, the pure hydrogen is collected by the cathode electrode; Specifically: the gas cracked by the cracking gas synthesis tower enters the plasma tower for reaction, and a positive electrode and a negative electrode are arranged in the tower to generate a plasma atmosphere and high-energy plasma under the action of an electric field; a porous medium is arranged between the positive and negative electrodes, and a catalyst is attached thereon, and a plurality of electrode bodies formed in this way are arranged in a honeycomb shape; H2S and NH3 gaseous substances are dissociated into H2, N2, and S in the electrode body; wherein the porous medium and the negative electrode have a mesh structure, and the porous medium and the negative electrode are both impregnated with a catalyst layer of NiO and CeO2, and the cerium / nickel ratio is between 5% and 20%, and they are bonded by dipping and coating and baking at 150°C, and the temperature of the plasma chamber is maintained at 150°C to 200°C and the pressure is 0.1MPa; The solution containing HCl dissolved in the liquid enters the anode electrode of the electrolysis device. After electrolysis, HCl produces H2, and pure hydrogen is collected by the cathode electrode; The cathode electrode material is selected from sponge lead; lead is plated on foam ceramics or mesoporous foam glass to prepare porous sponge lead; electrocatalyst is filled on foam ceramics or mesoporous foam glass; one of the electrocatalysts is filled on the foam nickel with foam nickel as a conductive skeleton; wherein the electrocatalyst is a mixed component of at least two of NiO, CuO, MgO, Re2O3, and PbO2; One side of the cathode electrode is chemically plated with an electrocatalyst mixture; wherein the electrocatalyst is a mixed component of at least two of NiO, CuO, MgO, Re2O3, and PbO2; The membrane material comprises an ion selective exchange resin membrane and a natural fibrous silicate mineral; The diaphragm material is tightly attached to the side of the cathode electrode without electrocatalyst under a certain pressure without leaving any gaps; The anode electrode is on the other side of the diaphragm. Specifically, a conductive coating with Pb(NO3)2 as a precursor is plated by chemical plating, and then a mixed solution of MnO2, CuO, graphite and carbon black is plated by electroplating to obtain an anode electrode layer.

2. The device for producing hydrogen and sulfur from industrial organic solid waste according to claim 1, characterized in that: The thickness of the diaphragm is 0.2 to 5.0 mm.

3. The device for producing hydrogen and sulfur from industrial organic solid waste according to claim 1, characterized in that: The device also includes a first pressure swing adsorption, which is used to remove by-product carbon dioxide from the gas separated by the gas-liquid separator. The by-product carbon dioxide is mixed with oxygen and enters the cracking gasification synthesis tower for further reaction. The mixed gas with carbon dioxide removed is subjected to a second pressure swing adsorption to obtain pure hydrogen. The gas removed by the second pressure swing adsorption is returned to the mixed gas for pressure swing adsorption treatment again.

4. The device for producing hydrogen and sulfur from industrial organic solid waste according to claim 1, characterized in that: The chlorine gas produced in the electrolysis device is passed into the alkali solution to obtain the by-product NaClO.

5. A method for producing hydrogen and sulfur from industrial organic solid waste, characterized in that: The method comprises: Step 1: Preparation of electrolysis device Select a cathode electrode material, and chemically plate a mixture of at least two of NiO, CuO, MgO, Re2O3, and PbO2 on one side of the material to obtain a highly active electrocatalytic cathode electrode layer; Apply a certain pressure to press the diaphragm material on one side of the highly active electrocatalytic cathode electrode layer, so that the diaphragm and the cathode electrode layer fit tightly together without leaving any gaps; Plating an anode electrode layer on the other side of the diaphragm; The cathode electrode layer, the diaphragm layer, and the anode electrode layer are baked and aged at 150°C to 200°C to form an integrated electrode system with a porous structure; Step 2: Treatment of industrial waste The cracked gas from the cracking gas synthesis tower enters the plasma tower for reaction, solid sulfur is recovered, and the gas enters the gas-liquid separator to separate the mixed gas with hydrogen for subsequent treatment; The liquid enters the anode electrode of the electrolysis device, and after electrolysis, pure hydrogen is collected by the cathode electrode.

6. The method for producing hydrogen and sulfur from industrial organic solid waste according to claim 5, characterized in that: In the step 1, sponge lead is selected as the cathode electrode material; lead is plated on foam ceramics or mesoporous foam glass to prepare porous sponge lead; electrocatalyst is filled on foam ceramics or mesoporous foam glass; and one of the electrocatalysts is filled on the foam nickel with foam nickel as the conductive skeleton; wherein the electrocatalyst is a mixed component of at least two of NiO, CuO, MgO, Re2O3, and PbO2.

7. The method for producing hydrogen and sulfur from industrial organic solid waste according to claim 5, characterized in that: In the step 1, the membrane material includes an ion selective exchange resin membrane and a natural fibrous silicate mineral.

8. The method for producing hydrogen and sulfur by utilizing industrial organic solid waste according to claim 5, characterized in that: In the step 1, the anode electrode layer is plated by chemically plating a conductive coating with Pb(NO3)2 as a precursor, and then electroplating a mixed solution of MnO2, CuO, graphite and carbon black to obtain the anode electrode layer.

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