CN110669560A - Green production process and production system for removing hydrogen sulfide in gas in combined chlor-alkali industry - Google Patents
Green production process and production system for removing hydrogen sulfide in gas in combined chlor-alkali industry Download PDFInfo
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- CN110669560A CN110669560A CN201911122192.2A CN201911122192A CN110669560A CN 110669560 A CN110669560 A CN 110669560A CN 201911122192 A CN201911122192 A CN 201911122192A CN 110669560 A CN110669560 A CN 110669560A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
Abstract
The invention relates to a green production process for removing hydrogen sulfide in gas in combined chlor-alkali industry and a production system thereof, and the technical scheme is that the green production process comprises a liquid exchange tank, a chlorination kettle, a filter, a first absorption tower, a second absorption tower and a chlor-alkali industry electrolytic bath filled with a sodium chloride solution, wherein gas outlets at the tops of the first absorption tower and the second absorption tower are clean natural gas outlets.
Description
Technical Field
The invention relates to a green production process for removing hydrogen sulfide in gas in combined chlor-alkali industry and a production system thereof, belonging to the technical field of removal of hydrogen sulfide in waste gas.
Background
Hydrogen sulfide (H)2S) is a colorless gas with the odor of rotten eggs, and has high toxicity, corrosiveness and inflammability. In industry, hydrogen sulfide gas is mainly generated in oil field exploitation, natural gas purification, coal gas purification and the like, and because the hydrogen sulfide gas is corrosive, industrial equipment such as pumps, pipelines and the like is often damaged, and various noble metal catalysts can be poisoned; when the concentration of hydrogen sulfide in air reaches 5ppm, it may injure human organs and cause death at 1000 ppm. Therefore, the method has very important significance for removing the hydrogen sulfide.
The mainstream processes for removing hydrogen sulfide in the industrial production at present include a claus method for recovering sulfur by gas-solid phase catalytic oxidation, an LO-CAT method for recovering sulfur by gas-liquid phase catalytic oxidation, a liquid phase absorption method for reacting an alcohol amine molecule with hydrogen sulfide, and the like. However, the claus process separates out the hydrogen sulfide in the gas for combustion and oxidation, and then feeds the hydrogen sulfide-containing gas back to the claus process, the gas component proportion and the reaction temperature need to be strictly controlled in the process, the process and the flow are complex, the reaction temperature is high, the claus process is only suitable for the high-sulfur hydrogen sulfide-containing gas, and is influenced by the reaction balance, and the desulfurization efficiency is limited to a certain extent; the LO-CAT method has complex catalyst proportion, is monopolized by foreign technologies for a long time, has large catalyst consumption, is only suitable for gas with low hydrogen sulfide content, and has higher operation cost; the regeneration of the absorbent by the liquid phase absorption method is always the bottleneck of the technology, and a large amount of waste liquid is easily generated to form secondary pollution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green production process for removing hydrogen sulfide in gas by combining chlor-alkali industry and a production system thereof, which can effectively solve the problems of low removal efficiency, complex process flow, high cost, waste pollution and the like in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry comprises a liquid exchange tank, a chlorination kettle, a filter, a first absorption tower, a second absorption tower and a chlor-alkali industry electrolytic tank filled with sodium chloride solution, wherein an alkali liquor outlet of the chlor-alkali industry electrolytic tank is connected with an inlet of the liquid exchange tank through a first valve, an outlet of the liquid exchange tank is respectively connected with an inlet at the upper part of the chlorination kettle through a second valve, is connected with an inlet at the upper part of the first absorption tower through a third valve and is connected with an inlet at the upper part of the second absorption tower through a fourth valve, air outlets at the tops of the first absorption tower and the second absorption tower are clean natural gas outlets, air inlets at the lower parts of the first absorption tower and the second absorption tower are hydrogen sulfide natural gas inlets, an outlet at the lower part of the first absorption tower is connected with an inlet of the liquid exchange tank through a fifth valve, an outlet at the lower part of the second absorption tower is connected with an inlet of the liquid exchange tank, the outlet at the lower part of the chlorination kettle is connected with the inlet of the filter through a seventh valve, the filtrate outlet of the filter is connected with the electrolyte inlet of the chlor-alkali industrial electrolytic cell through an eighth valve, and the chlorine outlet of the chlor-alkali industrial electrolytic cell is connected with the air inlet at the lower part of the chlorination kettle through a ninth valve.
Preferably, the electrolyte in the chlor-alkali industrial electrolytic cell is a saturated sodium chloride solution.
Preferably, the gas introduced from the gas inlets at the lower parts of the first absorption tower and the second absorption tower is natural gas containing hydrogen sulfide.
The invention relates to a green production process for removing hydrogen sulfide in gas in combined chlor-alkali industry, which comprises the following steps:
① opening a chlor-alkali electrolytic cell to electrolyze the saturated sodium chloride solution in the chlor-alkali electrolytic cell into hydrogen, chlorine and sodium hydroxide solution, sending the hydrogen out from the hydrogen outlet of the chlor-alkali industrial electrolytic cell, collecting and storing the hydrogen as an energy product for sale, sending the chlorine out from the chlorine outlet of the chlor-alkali industrial electrolytic cell to a chlorination kettle, and sending the sodium hydroxide solution to a first absorption tower and a second absorption tower through an alkali liquor outlet of the chlor-alkali industrial electrolytic cell via a liquor changing tank;
②, introducing natural gas containing hydrogen sulfide into the first absorption tower and the second absorption tower, reacting hydrogen sulfide in the natural gas with sodium hydroxide solution in the first absorption tower and the second absorption tower, and reacting the sodium hydroxide solution to generate sodium sulfide solution and obtain clean natural gas;
③ the generated sodium sulfide solution is conveyed to the chlorination kettle through the liquid exchange tank, the sodium sulfide solution reacts with the chlorine gas conveyed to the chlorination kettle from the chlorine gas outlet of the chlor-alkali industrial electrolytic cell to generate sulfur precipitate and sodium chloride solution, the sulfur precipitate and the sodium chloride solution are separated through a filter to respectively obtain sulfur powder and sodium chloride solution, the sulfur powder is conveyed out from the filter outlet and dried to be sold as chemical raw material products, and the sodium chloride solution is conveyed to the chlor-alkali industrial electrolytic cell from the filter outlet to be recycled as electrolyte.
The technological process of the invention relates to three chemical processes which are respectively as follows:
1. absorbing hydrogen sulfide in gas by using sodium hydroxide, wherein the reaction formula is
2NaOH+H2S＝Na2S+2H2O
The reaction is acid-base neutralization reaction, the reaction rate is high, and the reaction is thorough.
2. Chlorine is introduced into the generated sodium sulfide solution, and the reaction formula is
Na2S+Cl2＝2NaCl+S↓
The reaction is a nonmetal substitution reaction in the solution, the reaction speed in the solution is high, and the reaction is completely carried out because of the generation of precipitates.
3. The electrolytic reaction of the sodium chloride solution has the reaction formula of the total reaction in the electrolytic process
The reaction is the basic principle reaction of the electrolysis production in the chlor-alkali industry at present.
The three chemical reactions are all fast reactions, and high temperature and catalysts are not needed. And the metering amount of the three chemical reactions is balanced, the input substance into the circulating system is absorbed hydrogen sulfide, the output substances are hydrogen and sulfur, the amount of the absorbed hydrogen sulfide is just equal to the total amount of the output hydrogen and sulfur, all other substances participating in the reaction are kept balance in the circulation, other raw materials are not needed to be added, no waste is generated, and the closed circulation of green chemical production is realized.
The invention has the beneficial effects that:
the invention combines the gaseous hydrogen sulfide disposal of the chlor-alkali industry and the petrochemical industry, so that the production conditions are operated at normal temperature, no catalyst is needed, each step in the cyclic production is a controllable reaction with high conversion rate and less side reactions, the raw materials of each step are from the inside of the cyclic production process, the output substances are hydrogen and sulfur, the hydrogen and the sulfur can be sold as important products, no waste is generated in the process, no secondary pollution is generated, the method is a typical green chemical production mode, and the method is a technological innovation in the hydrogen sulfide removal technology.
Drawings
FIG. 1 is a schematic view of the structure of the production system of the present invention.
Fig. 2 is a block diagram of the process flow of the present invention.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
As can be seen from FIG. 1, the green production system for removing hydrogen sulfide from gas in combined chlor-alkali industry of the present invention comprises a liquid exchange tank 2, a chlorination reactor 3, a filter 4, a first absorption tower 5a, a second absorption tower 5b and a chlor-alkali industry electrolytic tank 1 filled with sodium chloride solution, wherein an alkali liquor outlet of the chlor-alkali industry electrolytic tank 1 is connected with an inlet of the liquid exchange tank 2 through a first valve 61, an outlet of the liquid exchange tank 2 is respectively connected with an inlet at the upper part of the chlorination reactor 3 through a second valve 62, connected with an inlet at the upper part of the first absorption tower 5a through a third valve 63, connected with an inlet at the upper part of the second absorption tower 5b through a fourth valve 64, gas outlets at the tops of the first absorption tower 5a and the second absorption tower 5b are clean natural gas outlets, gas inlets at the lower parts of the first absorption tower 5a and the second absorption tower 5b are hydrogen sulfide-containing natural gas inlets, an outlet at the lower part of the first absorption tower 5a is connected with an inlet of the liquid exchange tank 2 through a, an outlet at the lower part of the second absorption tower 5b is connected with an inlet of the liquid change tank 2 through a sixth valve 66, an outlet at the lower part of the chlorination reactor 3 is connected with an inlet of a filter 4 through a seventh valve 67, a filtrate outlet of the filter 4 is connected with an electrolyte inlet of the chlor-alkali industrial electrolytic cell 1 through an eighth valve 8, and a chlorine outlet of the chlor-alkali industrial electrolytic cell 1 is connected with an air inlet at the lower part of the chlorination reactor 3 through a ninth valve 69; the electrolyte in the chlor-alkali industrial electrolytic cell 1 is a saturated sodium chloride solution, three products are generated by electrolysis, namely hydrogen, chlorine and a sodium hydroxide solution, wherein the hydrogen is sent out from a hydrogen outlet of the chlor-alkali industrial electrolytic cell 1, collected and stored as an energy product for sale, the chlorine is sent out from a chlorine outlet of the chlor-alkali industrial electrolytic cell 1 to a chlorination reactor 3 as a raw material for reacting with the sodium sulfide solution, the sodium hydroxide solution is sent to a first absorption tower 5a and a second absorption tower 5b through an alkali liquor outlet of the chlor-alkali industrial electrolytic cell 1 to absorb hydrogen sulfide in the natural gas containing hydrogen sulfide, clean natural gas is obtained from the tops of the first absorption tower 5a and the second absorption tower 5b, the sodium hydroxide absorbs the saturated hydrogen sulfide to generate a sodium sulfide solution, the generated sodium sulfide solution is sent to the chlorination reactor 3, the sodium sulfide solution reacts with the chlorine sent into the chlorination reactor from the chlorine outlet of the chlor-alkali industrial electrolytic cell 1 to generate a sulfur precipitate and a sodium chloride solution, sulphur deposits and the separation that the sodium chloride solution passes through filter 4, obtains sulphur powder and sodium chloride solution respectively, and sulphur powder is sent out the drying from filter 4 export and is waited to sell as the industrial chemicals product, and the sodium chloride solution is sent into chlor-alkali industry electrolysis trough 1 from the filter export and is used as electrolyte circulation, and whole process forms closed, output hydrogen and sulphur to there is not the waste product to produce, except the electric energy, also need not consume other external raw materials, has accomplished green, clean production.
In order to ensure the using effect, a first natural gas inlet pipeline is arranged on an air inlet at the lower part of the first absorption tower 5a, and a tenth valve 610 is arranged on the first natural gas inlet pipeline; and a second natural gas inlet pipeline is arranged on an air inlet at the lower part of the second absorption tower 5b, and an eleventh valve 611 is arranged on the second natural gas inlet pipeline.
A first natural gas outlet pipeline is arranged on an air outlet at the top of the first absorption tower 5a, and a twelfth valve 612 is arranged on the first natural gas outlet pipeline.
A second natural gas outlet pipeline is arranged on a gas outlet at the top of the second absorption tower 5b, and a thirteenth valve 613 is arranged on the second natural gas outlet pipeline; the electrolyte in the chlor-alkali industrial electrolytic cell 1 is a saturated sodium chloride solution; the gas introduced from the gas inlets at the lower parts of the first absorption tower 5a and the second absorption tower 5b is natural gas containing hydrogen sulfide.
The charging of the sodium hydroxide solution of the two absorption towers and the discharging of the saturated sodium sulfide solution are realized by the liquid exchange tank 2, the absorption towers have two groups, one group can be used for one purpose and one group can be used for absorption, the other group can be used for liquid exchange, the series connection can also be realized by adjusting the opening and closing of each valve, when in specific work, the first valve 61 is opened, the sodium hydroxide solution produced after the electrolysis of the saturated sodium chloride solution is sent into the liquid exchange tank 2 through the alkali liquor outlet of the chlor-alkali industrial electrolytic bath 1, after the saturated sodium hydroxide solution is filled, the first valve 61 is closed, the third valve 63 and the fourth valve 64 are opened, the second valve 62, the fifth valve 65 and the sixth valve 66 are closed at the same time, the sodium hydroxide solution is sent into the first absorption tower 5a and the second absorption tower 5b through pipelines, the tenth valve 610 and the eleventh valve 611 are opened, the natural gas containing hydrogen sulfide is respectively sent into the first absorption tower 5a and the second absorption tower, the sodium hydroxide solution in the two absorption towers absorbs the hydrogen sulfide in the natural gas containing hydrogen sulfide, clean natural gas is obtained from the tops of the two absorption towers, the clean natural gas is discharged by opening and closing a twelfth valve 612 and a thirteenth valve 613, the sodium hydroxide absorbs the saturated hydrogen sulfide to generate sodium sulfide solution, a third valve 63 and a fourth valve 64 are closed, a fifth valve 65 and a sixth valve 66 are simultaneously opened, the saturated sodium sulfide solution is sent into a liquid changing tank 2, a second valve 62 is opened, a seventh valve 67 is closed, the sodium sulfide solution in the liquid changing tank is sent into a chlorination kettle 3, a ninth valve 69 is opened, chlorine gas generated by electrolyzing the saturated sodium chloride solution is sent into the chlorination kettle from a chlorine outlet of a chlor-alkali industrial electrolytic tank 1 to react to generate sulfur precipitate and sodium chloride solution, the seventh valve 67 is opened, the sulfur precipitate and the sodium chloride solution enter a filter 4 to be separated to respectively obtain sulfur powder and the sodium chloride solution, the sulfur powder is sent out from the outlet of the filter 4 and dried to be used as a chemical raw material product for sale, the eighth valve 68 is opened, and the sodium chloride solution is sent into the chlor-alkali industrial electrolytic cell 1 to be used as the electrolyte for recycling.
The invention relates to a green production process for removing hydrogen sulfide in gas in combined chlor-alkali industry, which comprises the following steps:
① opening the chlor-alkali electrolytic cell 1 to electrolyze the saturated sodium chloride solution in the chlor-alkali electrolytic cell into hydrogen, chlorine and sodium hydroxide solution, then sending the hydrogen out from the hydrogen outlet of the chlor-alkali industrial electrolytic cell 1 to collect and store the hydrogen as an energy product for sale, sending the chlorine out from the chlorine outlet of the chlor-alkali industrial electrolytic cell 1 to the chlorination kettle 3, and sending the sodium hydroxide solution to the first absorption tower 5a and the second absorption tower 5b through the alkali liquor outlet of the chlor-alkali industrial electrolytic cell 1 via the liquor changing tank 2;
②, introducing natural gas containing hydrogen sulfide into the first absorption tower and the second absorption tower, reacting hydrogen sulfide in the natural gas with sodium hydroxide solution in the first absorption tower and the second absorption tower, and reacting the sodium hydroxide solution to generate sodium sulfide solution and obtain clean natural gas;
③ the generated sodium sulfide solution is conveyed to the chlorination kettle 3 through the liquid exchange tank 2, the sodium sulfide solution reacts with the chlorine gas conveyed to the chlorination kettle from the chlorine gas outlet of the chlor-alkali industrial electrolytic cell 1 to generate sulfur precipitate and sodium chloride solution, the sulfur precipitate and the sodium chloride solution are separated through the filter 4 to respectively obtain sulfur powder and sodium chloride solution, the sulfur powder is conveyed out from the outlet of the filter 4 and dried to be sold as chemical raw material products, and the sodium chloride solution is conveyed to the chlor-alkali industrial electrolytic cell 1 from the outlet of the filter to be recycled as electrolyte.
The first absorption tower 5a and the second absorption tower 5b are prior art, such as high pressure absorption tower which can resist alkali corrosion, and can be conventional high pressure alkali-resisting absorption tower such as packed tower, bubble cap tower or sieve plate tower according to the production gas speed and scale. The absorption tower is used in the existing natural gas hydrogen sulfide removal liquid phase absorption method. The natural gas output pressure is generally 3-10 MPa, and the absorption tower is also an absorption tower suitable for corresponding pressure.
The liquid exchange tank 2 is a conventional alkali corrosion resistant high pressure storage tank, the volume of which is matched with the volume of the absorption liquid, for example, a polytetrafluoroethylene lining storage tank can be adopted, and the pressure resistance pressure of which is matched with the natural gas production pressure.
The filter 4 can adopt a medium-low rotating speed normal pressure centrifugal filter which is conventional equipment in chemical production.
The electrolytic bath 1 for the chlor-alkali industry is an electrolytic bath for the chlor-alkali industry and is a key device for producing sodium hydroxide, chlorine and hydrogen by electrolyzing sodium chloride at present. The method mainly comprises a single-pole ion membrane electrolytic cell, a forced circulation ion membrane electrolytic cell, a high-current-density natural circulation ion membrane electrolytic cell and the like, and the specific selection type is determined according to the production scale of natural gas and the content of hydrogen sulfide.
Compared with the prior art for removing hydrogen sulfide, the method has the advantages of simple operation, mild production conditions, suitability for the production of gases containing hydrogen sulfide with various concentrations in a completely closed manner, no waste production, no pollution, low energy consumption, low operation cost, capability of obtaining economic benefits and good social and economic benefits, is suitable for removing the hydrogen sulfide gas and simultaneously producing two important products of sulfur and hydrogen, and has wide application prospects in the fields of coal chemical industry, oil and gas field production, tail gas treatment and chemical production.
The specific application embodiment is as follows:
the natural gas produced by a certain natural gas well contains 5000 +/-500 ppm of hydrogen sulfide, the temperature is 15 +/-2 ℃, the pressure is 3 +/-0.1 MPa, the concentration of the treated hydrogen sulfide is less than or equal to 13ppm according to the requirement of national standard GB17820-2012 on the gas quality index of the hydrogen sulfide, and the treatment is carried out by using the process disclosed by the invention.
The first absorption tower 5a and the second absorption tower 5b both adopt a pressure-resistant 5MPa packed tower, and the packing is a PVC hollow sphere with the diameter of phi 50 mm. The capacity of the absorption liquid of a single tower is 2m3. The liquid change tank 2 adopts a volume of 2m3The pressure vessel of (3) is resistant to 5 MPa. The chlorination kettle 3 has a volume of 3m3The polytetrafluoroethylene lining stirred tank. The filter 4 adopts a centrifugal filter with the speed of 3000 r/min. The chlor-alkali industrial electrolytic cell 1 adopts an effective electrolytic volume of 2m3The diaphragm electrolytic cell of (1). The electrolyte in the electrolytic cell adopts saturated sodium chloride solution.
The production and implementation process is as follows:
1. when all the valves are determined to be in the closed state, the first valve 61 is opened, the sodium hydroxide solution generated by electrolysis in the chlor-alkali electrolysis cell 1 is filled in the change tank 2 until full, and the first valve 61 is closed.
2. The third valve 63 is opened, the sodium hydroxide solution in the change tank 2 is charged into the first absorption tower 5a, and the third valve 63 is closed.
3. The fourth valve 64 is opened, the sodium hydroxide solution in the liquid change tank 2 is charged into the second absorption tower 5b, and the fourth valve 64 is closed.
4. Opening a tenth valve 610 and a twelfth valve 612, allowing the natural gas containing hydrogen sulfide to pass through the first absorption tower 5a, enabling the hydrogen sulfide in the natural gas to react with the sodium hydroxide in the first absorption tower 5a to be absorbed, monitoring the content of the hydrogen sulfide in the outlet gas, when the content of the hydrogen sulfide in the outlet gas rises from 0, indicating that the sodium hydroxide in the absorption tower has basically reacted to generate the sodium sulfide, closing the tenth valve 610 and the twelfth valve 612 before the content of the hydrogen sulfide in the outlet gas rises to 10ppm, wherein the absorption saturation time of the absorption tower is about 7 hours, and the temperature of the reaction liquid in the absorption tower rises from about 15 ℃ to 65 ℃. The removal rate of the hydrogen sulfide is more than 99.8 percent through measurement and calculation. The content of the hydrogen sulfide in the outlet gas meets the requirement of national standard GB17820-2012 on the gas quality index of hydrogen sulfide.
5. The tenth valve 610 and the twelfth valve 612 are closed, the eleventh valve 611 and the thirteenth valve 613 are opened, and the absorption column is switched to the second absorption column 5 b. Since the first absorption tower 5a and the second absorption tower 5b are identical, the measurement and control conditions are also identical.
6. The fifth valve 65 is opened, the sodium sulfide solution produced by the reaction in the first absorption column 5a is transferred to the liquid-change tank 2, and the fifth valve 65 is closed.
7. The second valve 62 is opened, the sodium sulfide solution in the change-over tank 2 is moved into the chlorination reactor 3, and the second valve 62 is closed.
8. Opening the ninth valve 69, introducing chlorine gas generated in the chlor-alkali industrial electrolytic cell into the chlorination kettle 3, controlling the chlorine gas flow to be about 275L/min, measuring the sulfur ion content in the reaction solution, closing the ninth valve 69 when the sulfur ion measurement value is about 0, reacting for about 3 hours, and raising the temperature to about 85 ℃.
9. And opening the seventh valve 67, transferring the suspension of sodium chloride and sulfur generated in the chlorination kettle 3 into the filter 4, closing the seventh valve 67, filtering for 15min at 3000r/min by using the filter, removing the filter residues which are sulfur powder with the weight of about 100kg and the water content of about 30-40%, drying, and selling.
10. And opening an eighth valve 68, cooling the filtrate in the filter 4, transferring the filtrate into a chlor-alkali industrial electrolytic cell 1 for electrolysis, transferring the generated hydrogen into a hydrogen container for sale, transferring the generated chlorine into a chlorination kettle 3 for reaction, and transferring the generated sodium hydroxide solution into a liquid exchange tank 2.
11. And returning to the step 2, and entering the next working cycle.
12. Returning to step 5, after the second absorption column 5b is saturated, the valves 611 and 613 are closed, the valves 610 and 612 are opened, and the absorption column is switched to the first absorption column 5 a. Then, the sixth valve 66 is opened, the sodium sulfide solution produced by the reaction in the second absorption column 5b is transferred to the liquid-change tank 2, and the sixth valve 66 is closed. And (5) repeating the step (7) to the step (10), returning to the step (3) and entering the next working cycle.
It can be seen from the examples that the hydrogen sulfide removal rate in natural gas can reach 99.8% by using the process of the present invention. The outlet gas meets the requirements of national standard GB17820-2012 on the gas quality index of hydrogen sulfide, no three wastes are discharged in the production process, other raw materials are not needed to be input, sulfur powder and hydrogen can be produced, and the method is a closed-cycle green production process.
Claims (8)
1. A green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry is characterized by comprising a liquid exchange tank (2), a chlorination kettle (3), a filter (4), a first absorption tower (5a), a second absorption tower (5b) and a chlor-alkali industry electrolytic tank (1) filled with sodium chloride solution, wherein an alkali liquor outlet of the chlor-alkali industry electrolytic tank (1) is connected with an inlet of the liquid exchange tank (2) through a first valve (61), an outlet of the liquid exchange tank (2) is respectively connected with an inlet at the upper part of the chlorination kettle (3) through a second valve (62), is connected with an inlet at the upper part of the first absorption tower (5a) through a third valve (63), is connected with an inlet at the upper part of the second absorption tower (5b) through a fourth valve (64), and a gas outlet at the tops of the first absorption tower (5a) and the second absorption tower (5b) is a clean natural gas outlet, the gas inlet at the lower part of the first absorption tower (5a) and the second absorption tower (5b) is a gas inlet containing natural gas containing hydrogen sulfide, the outlet at the lower part of the first absorption tower (5a) is connected with the inlet of the liquid changing tank (2) through a fifth valve (65), the outlet at the lower part of the second absorption tower (5b) is connected with the inlet of the liquid changing tank (2) through a sixth valve (66), the outlet at the lower part of the chlorination kettle (3) is connected with the inlet of the filter (4) through a seventh valve (67), the filtrate outlet of the filter (4) is connected with the electrolyte inlet of the chlor-alkali industrial electrolytic tank (1) through an eighth valve (8), and the chlorine outlet of the chlor-alkali industrial electrolytic tank (1) is connected with the gas inlet at the lower part of the chlorination kettle (3) through a ninth valve (69).
2. The green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry of claim 1, wherein a first natural gas inlet pipeline is arranged on the gas inlet at the lower part of the first absorption tower (5a), and a tenth valve (610) is arranged on the first natural gas inlet pipeline.
3. The green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry of claim 1, wherein a second natural gas inlet pipeline is arranged on the gas inlet at the lower part of the second absorption tower (5b), and an eleventh valve (611) is arranged on the second natural gas inlet pipeline.
4. The green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry of claim 1, wherein a first natural gas outlet pipeline is arranged on a gas outlet at the top of the first absorption tower (5a), and a twelfth valve (612) is arranged on the first natural gas outlet pipeline.
5. The green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry of claim 1, wherein a second natural gas outlet pipeline is arranged on the gas outlet at the top of the second absorption tower (5b), and a thirteenth valve (613) is arranged on the second natural gas outlet pipeline.
6. A green production system for removing hydrogen sulfide from gas in combined chlor-alkali industry according to claim 1, characterized in that the electrolyte in said chlor-alkali industry electrolysis cell (1) is a saturated sodium chloride solution.
7. The green production system for removing hydrogen sulfide in gas in combined chlor-alkali industry of claim 1, wherein the gas introduced into the gas inlets at the lower parts of the first absorption tower (5a) and the second absorption tower (5b) is natural gas containing hydrogen sulfide.
8. A green production process for removing hydrogen sulfide in gas in combined chlor-alkali industry is characterized by comprising the following steps:
①, firstly opening the chlor-alkali electrolytic cell (1), electrolyzing the saturated sodium chloride solution in the chlor-alkali electrolytic cell into hydrogen, chlorine and sodium hydroxide solution, then sending the hydrogen out from the hydrogen outlet of the chlor-alkali industrial electrolytic cell (1), collecting and storing the hydrogen as an energy product for sale, sending the chlorine out from the chlorine outlet of the chlor-alkali industrial electrolytic cell to the chlorination kettle (3), and sending the sodium hydroxide solution to the first absorption tower (5a) and the second absorption tower (5b) through the alkali liquor outlet of the chlor-alkali industrial electrolytic cell (1) via the liquor changing tank (2);
②, introducing natural gas containing hydrogen sulfide into the first absorption tower and the second absorption tower, reacting hydrogen sulfide in the natural gas with sodium hydroxide solution in the first absorption tower and the second absorption tower, and reacting the sodium hydroxide solution to generate sodium sulfide solution and obtain clean natural gas;
③ the generated sodium sulfide solution is conveyed to the chlorination kettle (3) through the liquid exchange tank (2), the sodium sulfide solution reacts with the chlorine gas conveyed to the chlorination kettle from the chlorine gas outlet of the chlor-alkali industrial electrolytic cell to generate sulfur precipitate and sodium chloride solution, the sulfur precipitate and the sodium chloride solution are separated through the filter (4) to respectively obtain sulfur powder and sodium chloride solution, the sulfur powder is conveyed out from the outlet of the filter (4) to be dried and used as chemical raw material products for sale, and the sodium chloride solution is conveyed to the chlor-alkali industrial electrolytic cell (1) from the outlet of the filter to be recycled as electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911122192.2A CN110669560A (en) | 2019-11-15 | 2019-11-15 | Green production process and production system for removing hydrogen sulfide in gas in combined chlor-alkali industry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911122192.2A CN110669560A (en) | 2019-11-15 | 2019-11-15 | Green production process and production system for removing hydrogen sulfide in gas in combined chlor-alkali industry |
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| Publication Number | Publication Date |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285379A (en) * | 2020-03-17 | 2020-06-16 | 塔里木大学 | Vermiculite processing clean comprehensive utilization system and method |
| CN114367177A (en) * | 2022-01-14 | 2022-04-19 | 河南工程学院 | Green production method and device for removing hydrogen sulfide in industrial gas through two-step reaction |
| WO2024040703A1 (en) * | 2022-08-24 | 2024-02-29 | 湖南福尔程环保科技有限公司 | Resource utilization method for crude sodium sulfate |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285379A (en) * | 2020-03-17 | 2020-06-16 | 塔里木大学 | Vermiculite processing clean comprehensive utilization system and method |
| CN114367177A (en) * | 2022-01-14 | 2022-04-19 | 河南工程学院 | Green production method and device for removing hydrogen sulfide in industrial gas through two-step reaction |
| WO2024040703A1 (en) * | 2022-08-24 | 2024-02-29 | 湖南福尔程环保科技有限公司 | Resource utilization method for crude sodium sulfate |
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