CN114950117B - Industrial carbon sequestration system and method for absorbing carbon dioxide gas - Google Patents

Industrial carbon sequestration system and method for absorbing carbon dioxide gas Download PDF

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CN114950117B
CN114950117B CN202210369123.7A CN202210369123A CN114950117B CN 114950117 B CN114950117 B CN 114950117B CN 202210369123 A CN202210369123 A CN 202210369123A CN 114950117 B CN114950117 B CN 114950117B
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CN114950117A (en
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刘志盛
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China National Coal Group Corp
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Abstract

The invention relates to an industrial carbon sequestration system and method for absorbing carbon dioxide gas. The industrial carbon fixation system comprises a hydrogen supply unit, a sodium sulfate reduction unit, a sodium sulfide solution carbon dioxide absorption unit, a sodium carbonate treatment unit, a hydrogen sulfide treatment unit and a sulfuric acid hydrochloric acid preparation unit, wherein sodium sulfate, sodium chloride, hydrogen and water are subjected to reasonable process design to produce sodium bicarbonate, sulfur, sulfuric acid and hydrochloric acid, and the sodium sulfide solution absorbs carbon dioxide to separate out hydrogen sulfide so as to realize chemical carbon fixation of carbon dioxide; the hydrogen sulfide is converted to sulfuric acid and reacts with sodium chloride to produce sodium sulfate. The invention has wide raw material source, easy product storage and no limitation of the source and the manufacturing process of the organic carbon carrier; and can be used as an industrial basic raw material; the whole process has no high energy consumption processes such as compression, desorption, regeneration and the like; can provide a possible way for accelerating carbon neutralization industrialization; realizes the one-step integration of the carbon dioxide capture and solidification process and the integration of the device.

Description

Industrial carbon sequestration system and method for absorbing carbon dioxide gas
Technical Field
The invention relates to the technical field of carbon dioxide capture and storage, in particular to an industrial carbon fixation system and method for absorbing carbon dioxide gas.
Background
In order to realize carbon emission reduction, china is focused on developing solar energy and wind energy renewable energy sources, and aims to realize electric energy decarburization and greatly reduce carbon dioxide emission from the source. At present, wind energy and solar energy often face the difficulty of peak regulation and electricity abandonment, and increasingly urgent carbon emission reduction requirements and the abandonment of clean energy are avoided, so that the energy contradiction is highlighted. In addition to carbon abatement, a necessary means to achieve carbon neutralization is the manual removal of carbon dioxide, such as carbon sequestration and carbon dioxide capture and sequestration (CCUS). Although the emission of carbon dioxide generated by coal-fired power generation can be reduced by vigorously developing wind power, solar energy and nuclear power, if the carbon dioxide which is intensively emitted by the current industry can be solidified or sealed, the emission of the carbon dioxide in the atmosphere can be greatly reduced. In order to fully utilize clean electric energy, hydrogen is produced by electrolyzing water to form a way of phase-change electricity storage, capture and sealing of carbon dioxide are realized by utilizing hydrogen, a closed-loop zero-carbon CCUS industrial chain is formed, and the aim of human carbon neutralization is favorably realized at an early stage.
Since 2000, the design optimization of chemical absorption and regeneration processes, such as absorbent design, mass transfer equipment strengthening design, absorption-mineralization process design and other related works, has been intensively researched by the CCUS, and from the viewpoint of chemical element circulation and system energy balance in the global life cycle, a carbon dioxide capture process system is developed and integrated, so that the method for really realizing carbon capture and sequestration (CCUS) is realized. Currently, the intensity of human carbon dioxide emission reaches 364 hundred million tons every year, and in order to achieve the aim of carbon neutralization on time, the development of a carrier of carbon dioxide with wide raw materials and a low-energy-consumption and low-cost method for capturing and storing industrial fixed carbon are urgent tasks for realizing 'carbon neutralization'. The method utilizes electric energy or hydrogen energy, sodium sulfate and sodium chloride with rich reserves are used as raw materials to produce sodium sulfide, sodium carbonate and hydrogen sulfide are formed by absorbing carbon dioxide through a sodium sulfide solution, hydrogen sulfide gas is converted into solid sulfur or liquid sulfuric acid, the sodium carbonate can further absorb the carbon dioxide and convert the carbon dioxide into sodium bicarbonate, liquid-phase sulfuric acid or a solid-phase sulfur product is produced as a side product, the sulfuric acid reacts with the sodium chloride to obtain sodium sulfate and hydrochloric acid, the solid sodium sulfate can be sent to a sodium sulfate reduction step, and the sodium sulfide is converted through the sodium sulfate by taking the sodium chloride as the raw material and is linked to a carbon dioxide capture circulation flow. The method fully utilizes clean electric energy and hydrogen energy, achieves the purpose of collecting and storing carbon dioxide in a gas phase in solid-phase sodium carbonate or sodium bicarbonate, forms an industrialized low-carbon CCUS industrial chain integrated system, is an innovative industrial production method of soda ash, baking soda, sulfur, sulfuric acid and hydrochloric acid, improves the low and zero values of the CCUS industrial value, can fully utilize a large amount of industrial byproducts and sodium sulfate and sodium chloride products which are difficult to recycle, and achieves the industrial and environment-friendly effects of achieving multiple purposes.
The existing carbon capture and solidification integrated CCUS patent technology mostly focuses on biological methods, such as utilizing carriers of algae, bacteria and the like, and essentially utilizes the biological characteristics of photoautotrophy or photoheterotrophic carbon dioxide conversion of organisms; the non-biological carbon capture and solidification integrated patent technology mostly adopts a sodium carbonate and sodium hydroxide method. For example, the cn201010510906.X patent by katydi electric power corporation of wuhan was used for carbon dioxide absorption enrichment and separation by sodium carbonate; the Hangzhou Senjing atmospheric environment science and technology company utilizes sodium carbonate and an activating agent to capture and pyrolyze carbon dioxide in CN 201310038441.6; in CN202121202342.3, the Chinese Huaneng group clean energy technology research institute, inc. uses sodium carbonate and sodium hydroxide as raw materials to absorb, solidify and collect carbon dioxide; the patent CN201810686953.6 of beijing university of science and technology discloses a method for capturing carbon dioxide by using sodium hydroxide and sodium carbonate, but both methods use caustic soda and soda ash singly for chemical absorption of carbon dioxide, and if two bases need to be purchased and the use amount is large, the reliability, economy and low carbon of the method are greatly uncertain. Alston technology Limited integrates carbon dioxide capture and ammonia-soda process for producing sodium carbonate in CN201410021763.4, but the method is still the waiting soda process invented by Hou Debang, and the process uses ammonia and the production of ammonia needs to discharge more carbon dioxide. Therefore, the carbon neutralization method is a real carbon neutralization method by solving the problem of alkali sources and simultaneously avoiding the carbon dioxide additionally discharged from the alkali production links.
Disclosure of Invention
In order to solve the current situations of low efficiency, high cost and difficult popularization in the existing industrial method for capturing and storing carbon dioxide, the purpose of efficiently utilizing the increasing decarbonization clean power to capture and store the carbon dioxide is realized, the carbon emission of the raw material production of the existing chemical carbon dioxide absorption method is reduced, and simultaneously, a large amount of industrial by-products of low-value sodium sulfate and sodium chloride waste salt are converted into high-value products, thereby providing a possible way for accelerating the carbon neutralization process.
The invention is realized by the following steps:
an industrial carbon sequestration system for absorbing carbon dioxide gas comprises a hydrogen supply unit, a sodium sulfate reduction unit, a sodium sulfide solution absorption carbon dioxide unit, a sodium carbonate treatment unit and a hydrogen sulfide treatment unit;
the hydrogen produced by the hydrogen supply unit is connected with the sodium sulfate reduction unit through an output pipeline;
the sodium sulfate reduction unit reduces sodium sulfate into sodium sulfide by hydrogen, and the produced sodium sulfide is sent to a sodium sulfide solution to absorb carbon dioxide;
the unit for absorbing carbon dioxide by the sodium sulfide solution comprises absorbent solution preparation equipment, a carbon dioxide absorption tower/reactor, liquid-solid separation equipment, a slurry discharge pump and a solution circulating pump; the outlet of the carbon dioxide-containing raw material gas storage device is connected with a raw material gas inlet at the bottom of a carbon dioxide absorption tower/reactor, the exhaust gas of the carbon dioxide absorption tower/reactor is connected with a hydrogen sulfide treatment unit or another group of carbon dioxide absorption tower/reactor through an output pipeline, a slurry outlet at the bottom of the carbon dioxide absorption tower/reactor is connected with a raw material inlet of a liquid-solid separation device through a pipeline, a clear liquid outlet of the liquid-solid separation device is connected with an inlet of a solution circulating pump through a pipeline, a slurry outlet of the liquid-solid separation device is connected with a raw material inlet of a sodium carbonate treatment unit through a slurry discharge pump, an outlet of the solution circulating pump is connected with a raw material inlet of a solution preparation device through a pipeline, the exhaust gas of the solution preparation device is connected with the raw material gas inlet of the hydrogen sulfide treatment unit through a pipeline, sodium sulfide is injected into an absorbent solution preparation device through a pipeline, a liquid phase outlet of the solution preparation device is connected with a liquid phase inlet at the upper part of the carbon dioxide absorption tower/reactor through an output pipeline, and deionized water injection pipelines are arranged at the middle parts of the carbon dioxide absorption tower/reactor and the solution preparation device;
the sodium carbonate processing unit is provided with sodium carbonate/sodium bicarbonate slurry processing equipment, the slurry discharged by the liquid-solid separation equipment through the slurry discharge pump is crystallized, dried or decomposed, the produced liquid-phase material and gas-phase material are respectively sent to the sodium sulfide solution absorption carbon dioxide unit through pipelines, and the solid-phase product can be packaged as a product;
the hydrogen sulfide treatment unit comprises a sulfur preparation device and/or a sulfuric acid preparation device and/or a sodium hydroxide washing and absorbing hydrogen sulfide device, and the exhaust gas of the hydrogen sulfide treatment unit is decarburization and desulfurization exhaust gas; the sulfur preparation device converts hydrogen sulfide into a sulfur product, and the sulfuric acid preparation device combusts, oxidizes, dissolves and absorbs the hydrogen sulfide and oxygen to prepare a sulfuric acid product.
Preferably, the system further comprises a sulfuric acid hydrochloric acid unit, the sulfuric acid hydrochloric acid unit is provided with a sulfuric acid hydrochloric acid device, sulfuric acid reacts with sodium chloride to produce sodium sulfate and hydrochloric acid, and sodium sulfate crystals are dried and then return to the sodium sulfate reduction unit for recycling.
Preferably, the oxygen produced by the hydrogen supply unit is connected with the hydrogen sulfide treatment unit through an output pipeline.
Preferably, the absorption tower/reactor of the unit for absorbing carbon dioxide by the sodium sulfide solution is a carbon dioxide absorption tank, a stirring kettle or a belt
One or more than one carbon dioxide absorption tower of solid phase raw materials; the container for preparing the solution is provided with a mixing or stirring device; the pipeline and equipment of the unit for absorbing carbon dioxide by sodium sulfide adopt acid and alkali corrosion resistant materials or linings; a raw material gas inlet or a discharge gas outlet of the carbon dioxide absorption tower/reactor is provided with an air blower or an induced draft fan according to the requirements of the operation pressure, the processing load and the air space velocity of the absorption tower; the carbon dioxide absorption tower/reactor vent gas is provided with a demister and a cooler.
An industrial carbon fixation method for absorbing carbon dioxide gas comprises the following steps:
(1) Electrolyzing water to produce hydrogen: electrolyzing water into hydrogen, and sending the hydrogen to a sodium sulfate reduction unit through a pipeline;
(2) Reduction of sodium sulfate: reducing a sodium sulfate raw material into a sodium sulfide product by hydrogen at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously operated; after the process water is processed into deionized water, the deionized water is sent to the step (1) of electrolyzing water to prepare hydrogen or the step (3) of preparing a sodium sulfide solution;
(3) Preparing an absorbent solution: in solution preparation equipment with stirring or mixing function, mixing clear liquid of liquid-solid separation equipment, deionized water and sodium sulfide to prepare an absorbent solution used by a carbon dioxide absorption tower/reactor; collecting hydrogen sulfide gas separated out during solution preparation and then sending the hydrogen sulfide gas to a hydrogen sulfide treatment unit; the prepared absorbent solution is sent into a carbon dioxide absorption tower/reactor of a sodium sulfide solution absorption carbon dioxide unit;
(4) Introducing raw gas containing carbon dioxide into the carbon dioxide absorption tower/reactor, wherein the temperature of deionized water injected into the absorbent is lower than that of the solvent; selecting absorbent solutions with different pH values and components according to the concentration of carbon dioxide and the oxygen content in the feed gas;
(5) Measuring the PH value of the solution at each part in the absorption tower/reactor in the step (4) to judge the reaction progress, the solution components and the carbon dioxide absorption capacity of each part in the absorption tower, and when the PH value is>At 9.4, the crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S; when the pH is 8.3-9.4, continuously introducing carbon dioxide, wherein the crystalline solid is a mixture of sodium carbonate and sodium bicarbonate; when PH =8.3, the crystalline solid is sodium bicarbonate and the solution no longer has the capacity to absorb carbon dioxide; after the solid-liquid mixture after absorbing the carbon dioxide passes through liquid-solid separation equipment, the slurry with high solid content is transferred into a sodium carbonate or sodium bicarbonate treatment unit; returning the clear liquid with low solid content after liquid-solid separation to the step (3) for supplementing sodium sulfide and coolingCondensing water to prepare an absorbent solution; the produced hydrogen sulfide gas is sent to a hydrogen sulfide treatment unit;
(6) Packaging sodium carbonate or bicarbonate product: drying the slurry separated in the step (5), and then respectively packaging the dried slurry according to the product components; sodium carbonate and carbon dioxide are generated after sodium bicarbonate is decomposed, the sodium carbonate is used as a product for packaging, and the generated carbon dioxide is collected and then sent to the step (4) to be used as raw material gas.
(7) Hydrogen sulfide and oxygen combustion reaction: the sodium sulfide absorbs the gas containing hydrogen sulfide discharged from the carbon dioxide unit, and the gas and the oxygen prepared by the hydrogen supply unit are combusted and oxidized to prepare a sulfuric acid product, the sulfuric acid is put into the sulfuric acid-to-hydrochloric acid unit, the heat generated by the combustion of the hydrogen sulfide is used for heating the reducing gas and the sodium sulfate solid in the sodium sulfate reducing unit, and the gas after desulfurization is discharged into the atmosphere after being qualified;
(8) Hydrogen sulfide electrolysis reaction: the hydrogen sulfide in the step (7) can also be sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide;
preferably, the industrial carbon sequestration method further comprises the steps of:
(9) Preparing hydrochloric acid by using sulfuric acid: industrial sodium chloride and sulfuric acid are used as raw materials, sodium sulfate and hydrogen chloride gas are produced, the hydrogen chloride gas is absorbed to prepare hydrochloric acid solution, and the sodium sulfate is crystallized and dried and then is sent to a sodium sulfate reduction unit.
Preferably, the oxygen produced by the hydrogen production by water electrolysis in step (1) is sent to the hydrogen sulfide treatment unit through an output pipeline.
Preferably, the sodium sulfide cooling mode in the step (2) adopts chilling water to directly mix and cool, and is connected with a subsequent downstream sodium sulfide solution preparation unit.
Preferably, the temperature of the absorbent in the step (3) is 30-90 ℃; the concentration of sodium sulfide and the concentration of sodium carbonate are determined according to the concentration of carbon dioxide and the oxygen content in the feed gas: in the absorbent solution, the content of sodium sulfide in each 100g of water is 0-0.735mol, and the content of sodium carbonate in each 100g of water is 0-0.46mol; the operation temperature of the carbon dioxide absorption tower/reactor and the absorbent solution preparation equipment and the concentration of the solid phase content of the solution can be adjusted by adjusting the injection amount of the deionized water. The operating pressure of the carbon dioxide absorption unit is-0.1 to 3MPa.
Preferably, the sodium sulfide in the step (3) is added into the solution preparation equipment in a mode of directly adding solid or supplementing high-concentration solution.
Preferably, step (4) can combine more than two sodium sulfide solution absorption carbon dioxide units in series, and the exhaust gas of the former carbon dioxide absorption tower/reactor is connected with the raw material gas inlet which is conveyed to the latter carbon dioxide absorption tower/reactor through an output pipeline; a part of clear liquid discharged from the latter liquid-solid separation equipment is sent to the raw material inlet of the former solution preparation equipment.
Preferably, the sulfuric acid obtained in the step (7), the sulfur produced by the indirect electrolysis in the step (8) and the hydrochloric acid obtained in the step (9) are used as final products for product packaging.
The technical effects are as follows:
compared with the prior carbon capture and sealing method, the industrial carbon fixation system provided by the invention has the following advantages: due to the adoption of
The material is sodium sulfate, sodium chloride, hydrogen and water; the product is sodium bicarbonate, sulfur, sulfuric acid, hydrochloric acid; sodium sulfide is prepared by reducing sodium sulfate with hydrogen, and chemical carbon fixation of carbon dioxide is realized by absorbing carbon dioxide with a sodium sulfide solution to separate out hydrogen sulfide; the circulation process of preparing sulfuric acid by hydrogen sulfide and reacting with sodium chloride is adopted, and the process of taking sodium chloride as a raw material carrier is opened, so that the one-step integration of the carbon dioxide capturing and curing process and the integration of the device are realized. Sodium sulfate and sodium chloride as raw materials can be widely sourced from the natural world, sodium sulfate is particularly widely available in Chinese resources, accounts for over 95 percent of the worldwide reserves, and the sodium sulfate and sodium chloride as byproducts in the industrial field can be applied. The present invention is not limited by the source and manufacturing process of the organic carbon support, such as syngas, lipids, alcohols, esters, etc.
The sodium carbonate or sodium bicarbonate product produced by the invention can be used as an industrial basic raw material, and the chemicals are non-flammable and explosive and are suitable for being exposed to air or buried and stored in the ground and other natural conditions for a long time. The invention also produces high-purity hydrogen sulfide which is further converted into sulfur and sulfuric acid, the chemicals are not only important basic acid-base chemical raw materials, but also can be stored at normal pressure, and the elemental sulfur is easier to store in seawater; if the sodium chloride raw material is used as a carrier, the sodium chloride raw material reacts with the intermediate product sulfuric acid to produce sodium sulfate and hydrochloric acid, the sodium sulfate is circulated into the sodium sulfate reduction unit and is circulated again to absorb and solidify carbon dioxide, and thus a process circulation path using the sodium chloride as the raw material can be formed. The produced sulfur, sulfuric acid and hydrochloric acid can be used as industrial basic raw materials of metallurgy, chemical industry, nonferrous industry, electronic industry and the like.
Compared with the common carbon fixation process of absorbing carbon dioxide by a sodium hydroxide solution in the prior art, the method avoids the step of preparing caustic soda by electrolyzing sodium chloride and producing chlorine, and the chlorine is more toxic than sulfur and is easier to store than sulfur; the requirement of sodium chloride electrolysis on the purity of raw material salt and water is strict, and compared with the hydrogen production by water electrolysis, the method has high voltage and energy consumption and complex process; chlorine gas produced by the anode of the electrolytic sodium chloride is easy to dissolve in electrode liquid to form sodium hypochlorite by-products, and the reaction process and the separation process are controlled complicatedly; the invention adopts electrolytic water to prepare hydrogen, the hydrogen reduces sodium sulfate to produce sodium sulfide, the sodium sulfide solution absorbs carbon dioxide to replace and desorb hydrogen sulfide, the hydrogen sulfide is fully combusted and fired into sulfuric acid, the sulfuric acid reacts with sodium chloride to prepare hydrochloric acid, each process is reaction with few byproducts, the control is simple, and the product purity is high. The hydrogen supply system can also utilize solar energy and wind energy to electrolyze to produce hydrogen or coal, petroleum, natural gas and biomass to produce hydrogen, the hydrogen source is wide, and reducing gases such as CO and methane can be used for replacing the hydrogen source, so that the method has wide applicability; and the sodium hydroxide can be prepared only by an electrolytic method, the electrochemical reaction and the stronger absorption-discharge thermochemical reaction have poor coupling, and the whole energy utilization process is difficult to optimize.
The method can simultaneously produce high-purity sodium carbonate or sodium bicarbonate products, is different from the soda process by a combined alkali method or an ammonia-soda method, does not need the participation of high-energy product liquid ammonia in the process, and does not produce other salt products as a byproduct in the production of the soda; the thermal decomposition of sodium bicarbonate and ammonium bicarbonate is not needed for the circulation of carbon dioxide and ammonia, a large amount of mother liquor is not needed for evaporation concentration and cooling crystallization, and the overall investment and energy consumption are low. The sodium carbonate treatment unit can selectively produce sodium carbonate or sodium bicarbonate products according to requirements.
The invention is different from sulfur and sulfuric acid devices in natural gas, petroleum and coal chemical industry, the sulfur or sulfuric acid products produced by the method have sulfur elements from sodium sulfate instead of hydrogen sulfide in waste gas produced by crude oil or coal processing; the hydrogen sulfide processing unit can also be set as a process for producing sulfur and hydrogen by electrolyzing hydrogen sulfide indirectly; hydrogen can be sent to a sodium sulfate reduction unit for recycling; the sulfur produced by electrolysis can also be oxidized by pure oxygen to prepare sulfuric acid, and the released heat can be used for reducing and heating sodium sulfate; compared with other hydrogen sulfide treatment methods, the method can integrally reduce the energy consumption of the process; the hydrogen sulfide processing unit can also be set as a process for producing sulfur and hydrogen by electrolyzing hydrogen sulfide indirectly; hydrogen can be sent to a sodium sulfate reduction unit for recycling; the sulfur produced by electrolysis can also be oxidized by pure oxygen to prepare sulfuric acid, and the released heat can be used for reducing and heating sodium sulfate; compared with other hydrogen sulfide treatment methods, the method can integrally reduce the energy consumption of the process. The hydrogen sulfide treatment unit can be provided with a sulfur device or a sulfur device prepared by electrolyzing hydrogen sulfide as required, and can also continuously oxidize to prepare sulfuric acid so as to respectively produce high-purity sulfur or concentrated sulfuric acid products, and the load of the device and the distribution of the products are easy to control and allocate;
the hydrogen production by electrolyzing water can produce pure oxygen, the hydrogen sulfide sulfur or sulfuric acid unit of the system can use the pure oxygen to burn hydrogen sulfide, the conversion rate of hydrogen sulfide is high, the temperature generated by burning is high, the heat recovery rate is high, and the system can be coupled with a sodium sulfate reduction unit; the product water produced by the sodium sulfate reduction unit and the hydrogen sulfide treatment unit can be used as electrolyzed water, a sodium sulfide solution carbon dioxide absorption unit and supplementary water for absorbing carbon dioxide by a sodium carbonate solution, so that the consumption of system water is reduced;
the invention can treat carbon dioxide waste gas with wide sources, such as flue gas directly discharged by coal-fired power plants, chemical and metallurgical industrial boilers, enriched carbon dioxide gas and the like, and simultaneously absorbs and solidifies heavy metal ions such as sulfur dioxide, sulfur trioxide, lead, cadmium, mercury, arsenic and the like in the waste gas by absorbing and solidifying the carbon dioxide by utilizing the sodium sulfide.
Compared with the low-temperature methanol washing and the organic amine method for removing the carbon dioxide, the method has the advantages that the operation temperature is high, the liquid-phase operation temperature can be kept between 0 and 100 ℃, the higher the temperature is, the higher the decarburization efficiency is, the smaller the energy consumption is, and a refrigeration process and equipment do not need to be prepared;
the method does not need a solvent regeneration process, the sodium bicarbonate thermal decomposition unit for producing sodium carbonate decomposes according to the demand of sodium hydroxide for washing hydrogen sulfide, and the usage depends on the removal efficiency of hydrogen sulfide in the hydrogen sulfide separation unit; the method does not need a large amount of circulation of the solution, and the amount of mother liquor separated by the sodium bicarbonate can be selectively evaporated or the mother liquor can be reused according to the fluidity and the removal condition of the product mixture; the change of the operation pressure has little influence on the process of chemically absorbing the carbon dioxide, the method does not relate to the operation of flash evaporation for desorbing the carbon dioxide, and the loss of the pressure energy is little.
Compared with a solvent physical absorption method, the method does not need flash evaporation decarburization, hydrogen sulfide concentration, solvent regeneration and solvent rectification
The investment cost is reduced by corresponding pipelines and equipment such as a tower, a heat exchanger, a tank, a pump and the like; the method is a chemical absorption process, the process and the operation are simple, and the removal efficiency of carbon dioxide and hydrogen sulfide is high; the invention is a thermal process, and the sodium sulfate reduction, sodium bicarbonate decomposition and limestone calcination processes can be coupled with a high-temperature heat source of a conversion device and a sulfuric acid and sulfur device; solvent of the invention
The water solution is sodium sulfide, sodium carbonate, sodium hydroxide and the like, which are all inflammable and explosive chemicals, the liquid leakage of the equipment pipeline can not cause fire explosion accidents, and the toxicity of the three substances is less than that of methanol and organic amine; compared with low-temperature methanol washing and organic amine removal methods, the method removes the carbon dioxide by carbonate ions, and realizes the integration of one-step capture and storage of the carbon dioxide and the device.
Compared with the industrial fixed carbon for producing methanol by reducing carbon dioxide with hydrogen, the method for fixing the same carbon dioxide consumes 33% less hydrogen than the methanol route, and correspondingly, the investment of photovoltaic power generation and hydrogen production is greatly reduced; the methanol method for carbon fixation needs pure carbon dioxide, needs a carbon capture device for carbon dioxide enrichment purification and deoxidization, and the method can directly absorb the mixed gas oxygen-containing carbon dioxide feed gas, does not need to build a high-energy-consumption carbon capture device for investment, and exerts the advantage of the method of integrating carbon capture and solidification; in the carbon fixation synthesis by the methanol method, a methanol device needs a special synthesis catalyst and is a fixed bed reaction with high pressure, the operation is limited by the proportion of hydrogen and carbon dioxide, the investment and process cost of the methanol device are higher than those of a sodium sulfide device, the production of sodium sulfide is not limited by the special catalyst, and the production cost of sodium sulfide is greatly reduced by adopting a hydrogen gas phase fluidization reduction sodium sulfate production technology; compared with the prior art in terms of economy, the method consumes the same amount of hydrogen for carbon fixation, and the economic value of the sodium bicarbonate and the sulfuric acid produced by the sodium sulfide method is higher than that of methanol; through theoretical calculation, equivalent hydrogen is consumed for carbon fixation, the generated methanol and hydrogen sulfide have similar calorific values, but sodium sulfide is superior to methanol in storage and transportation aspects in analysis from the storage and transportation aspects; by integrating the analysis of the carbon dioxide carbon fixation net effect of the carbon element in the whole life cycle, the carbon fixation effect of methanol can be lost after the methanol is used as an energy source, and after hydrogen sulfide or sulfur produced by the Na2S carbon fixation is used as an energy source, the carbon fixation effect is not influenced because the sodium bicarbonate serving as a carbon fixation product still exists, and if the sodium bicarbonate does not enter the atmosphere for circulation any more, the carbon dioxide can be sealed and stored as a permanent product; the sodium bicarbonate can be coupled with the artificial biological carbon fixation phase technology, can accelerate the secondary transfer of carbon dioxide to carbohydrate, and improves the carbon fixation efficiency of biological photosynthesis.
Drawings
The invention is further described below with reference to the accompanying drawings. Wherein:
FIG. 1 is a schematic illustration of an alternative material input-output of the present invention;
FIG. 2 is a schematic diagram of an alternative material input-output of the present invention;
FIG. 3 is a schematic process flow diagram of the present invention;
FIG. 4 is a schematic process flow diagram of example 1 of the present invention;
FIG. 5 is a schematic process flow diagram of example 2 of the present invention;
FIG. 6 is a schematic process flow diagram of example 3 of the present invention;
FIG. 7 is a schematic process flow diagram of example 4 of the present invention;
FIG. 8 is a schematic process flow diagram of example 5 of the present invention;
FIG. 9 is a schematic process flow diagram of example 6 of the present invention;
FIG. 10 is a schematic process flow diagram of example 7 of the present invention;
FIG. 11 is a schematic process flow diagram of example 8 of the present invention;
FIG. 12 is a schematic process flow diagram of example 9 of the present invention;
FIG. 13 is a schematic process flow diagram of example 10 of the present invention;
FIG. 14 is a schematic process flow diagram of example 11 of the present invention;
FIG. 15 is a schematic process flow diagram of example 12 of the present invention;
FIG. 16 is a schematic process flow diagram of example 13 of the present invention;
FIG. 17 is a schematic process flow diagram of example 14 of the present invention;
FIG. 18 is a schematic process flow diagram of example 15 of the present invention;
FIG. 19 is a schematic connection diagram of a sodium sulfide absorption carbon dioxide unit plant;
FIG. 20 is a schematic diagram showing the connection of two sets of sodium sulfide absorption carbon dioxide unit facilities.
Detailed Description
In order to facilitate understanding of the present invention, the following description of the specific implementation steps and process flow will be described in detail with reference to the specific embodiments of the present invention, which are further illustrative and not restrictive of the industrial carbon sequestration system and process for absorbing carbon dioxide gas described in the present invention. It is obvious that the embodiments described are a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art, based on the embodiments of the present invention, will be able to obtain all other embodiments without inventive step, and all other embodiments are within the scope of the present invention. Examples 1 to 17 are decarburization processes in which the oxygen content of the mixed gas is less than 4.3%, and the differences are sodium carbonate, sodium bicarbonate, sulfur, sulfuric acid, and the upward extension of the raw material sodium chloride; example 18 is a decarbonization process with an oxygen content greater than 4.3%, and the process with an oxygen content greater than 4.3% is not listed in the product flow.
Example 1
See fig. 3, 4 and 19.
As shown in fig. 3, an industrial carbon sequestration system for absorbing carbon dioxide gas includes a hydrogen supply unit, a sodium sulfate reduction unit, a sodium sulfide solution absorption carbon dioxide unit, a sodium carbonate treatment unit, a hydrogen sulfide treatment unit, and a sulfuric acid hydrochloric acid production unit.
The hydrogen produced by the hydrogen supply unit is connected with the sodium sulfate reduction unit through an output pipeline;
the sodium sulfate reduction unit reduces sodium sulfate into sodium sulfide by hydrogen, and the produced sodium sulfide is sent to a sodium sulfide solution to absorb carbon dioxide;
as shown in fig. 19, the unit for absorbing carbon dioxide by sodium sulfide solution includes an absorbent solution preparation device 4, a carbon dioxide absorption tower/reactor 1, a sodium bicarbonate liquid-solid separation device 2, a slurry discharge pump 6, and a solution circulation pump 3; an outlet of the carbon dioxide-containing raw material gas storage device is connected with a raw material gas inlet at the bottom of a carbon dioxide absorption tower/reactor, the discharged gas of the carbon dioxide absorption tower/reactor is connected with a hydrogen sulfide treatment unit 5 through an output pipeline, a slurry outlet at the bottom of the carbon dioxide absorption tower/reactor 1 is connected with a raw material inlet of a liquid-solid separation device 2 through a pipeline, a clear liquid outlet of the liquid-solid separation device 2 is connected with an inlet of a solution circulating pump 3 through a pipeline, a slurry outlet of the liquid-solid separation device 2 is connected with a raw material inlet of a sodium carbonate treatment unit through a slurry discharge pump 6, an outlet of the solution circulating pump 3 is connected with a raw material inlet of a solution preparation device 4 through a pipeline, the discharged gas of the solution preparation device is connected with a raw material gas inlet of the hydrogen sulfide treatment unit 5 through a pipeline, sodium sulfide is injected into an absorbent solution preparation device 4 through a pipeline, a liquid phase outlet of the solution preparation device is connected with a liquid phase inlet at the upper part of the carbon dioxide absorption tower/reactor 1 through an output pipeline, and deionized water filling pipelines are arranged at the middle parts of the carbon dioxide absorption tower/reactor 1 and the solution preparation device 4;
in fig. 3, the sodium carbonate processing unit is configured with a sodium carbonate/sodium bicarbonate slurry processing device, the slurry discharged from the liquid-solid separation device through the slurry discharge pump is crystallized, dried or decomposed, the produced liquid-phase material and gas-phase material are respectively sent to the sodium sulfide solution absorption carbon dioxide unit through pipelines, and the solid-phase product can be packaged as a product;
the hydrogen sulfide treatment unit comprises a sulfur preparation device and/or a sulfuric acid preparation device and/or a sodium hydroxide washing and absorbing hydrogen sulfide device, and the exhaust gas of the hydrogen sulfide treatment unit is decarburization and desulfurization exhaust gas; the sulfur preparation device converts hydrogen sulfide into a sulfur product, and the sulfuric acid preparation device combusts, oxidizes, dissolves and absorbs the hydrogen sulfide and oxygen to prepare a sulfuric acid product.
The sulfuric acid hydrochloric acid unit is provided with a sulfuric acid hydrochloric acid preparation device, sulfuric acid and sodium chloride react to produce sodium sulfate and hydrochloric acid, and the sodium sulfate is crystallized and dried and then returns to the sodium sulfate reduction unit for recycling.
The reactor of the unit for absorbing carbon dioxide by sodium sulfide solution comprises a carbon dioxide absorption tank, a stirring kettle and a carbon dioxide with solid-phase discharge
One or more of the carbon absorption towers; the container for preparing the solution is provided with a mixing or stirring device; absorption of carbon dioxide monomer by sodium sulfide
The element pipeline and the equipment adopt acid and alkali corrosion resistant materials or linings. A raw material gas inlet or a discharge gas outlet of the carbon dioxide absorption tower/reactor is provided with an air blower or an induced draft fan according to the requirements of the operation pressure, the processing load and the air space velocity of the absorption tower; the exhaust gas of the carbon dioxide absorption tower/reactor is provided with a demister and a cooler.
As shown in fig. 4, the present embodiment includes the following steps in practical use:
1. electrolyzing water to produce hydrogen: electrolyzing water into hydrogen, delivering the hydrogen to a sodium sulfate reduction unit through a pipeline, delivering part of oxygen generated by electrolysis to a hydrogen sulfide treatment unit for sulfur recovery, and taking the rest oxygen as an oxygen product.
2. Reduction of sodium sulfate: hydrogen generated by electrolysis enters a sodium sulfate reduction unit, a sodium sulfate raw material is reduced into a sodium sulfide product at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously carried out, and the produced chemical industry
The temperature of the process condensate water is controlled to be about 90 ℃, the temperature of the produced sodium sulfide solid product is controlled to be about 100 ℃, the sodium sulfide solid product and the sodium sulfide solid product are sent to the next sodium sulfide solution preparation process, and meanwhile, the dissolving and heating energy sources are saved. More produced process water can be sent to the hydrogen production process by electrolyzing water after being treated by a reverse osmosis membrane.
3. Preparing an absorbent solution: preparing sodium sulfide solid and process condensate water into a high-concentration sodium sulfide solution; the cooling mode of sodium sulfide adopts chilling water to directly mix and cool. Collecting hydrogen sulfide gas separated out during solution preparation and then sending the hydrogen sulfide gas to a hydrogen sulfide treatment unit; the prepared absorbent solution is sent into a carbon dioxide absorption tower/reactor of a sodium sulfide solution absorption carbon dioxide unit. In order to accelerate the formation of high-temperature and high-concentration sodium sulfide solution, solution preparation can be carried out in a container with a slight stirring device, the sodium sulfide adopts a mode of directly adding solids, the sodium sulfide solution can be prepared into a concentrated solution at about 90 ℃, the content of the sodium sulfide in 100g of water is 0.0735mol, the content of sodium carbonate is 0.46mol, and the operating pressure of a carbon dioxide absorption unit is-0.1 MPa; preparing an absorbent solution used by the carbon dioxide absorption tower/reactor; collecting hydrogen sulfide gas separated out during solution preparation and then sending the hydrogen sulfide gas to a hydrogen sulfide treatment unit; the prepared absorbent solution is sent into a carbon dioxide absorption tower/reactor of a sodium sulfide solution absorption carbon dioxide unit; the operation temperature of the carbon dioxide absorption tower/reactor and the absorbent solution preparation equipment and the concentration of the solid phase content of the solution can be adjusted by adjusting the injection amount of the deionized water.
4. Introducing raw gas containing carbon dioxide into the carbon dioxide absorption tower/reactor, and injecting deionized water temperature of absorbent
A temperature below the solvent; absorbent solutions with different pH values and components are selected according to the concentration of carbon dioxide and the oxygen content in the raw material gas, the higher the concentration of the carbon dioxide in the raw material gas is, the lower the oxygen content is, the higher the concentration of sodium sulfide in the absorbent solution is, and the lower the concentration of sodium carbonate is; the lower the carbon dioxide concentration in the feed gas, the higher the oxygen content, and the lower the sodium sulfide concentration in the absorbent solution, the higher the sodium carbonate concentration.
5. Measuring the PH value of the solution at each part in the absorption tower/reactor in the step (4) to judge the reaction progress of each part in the absorption tower
Degree, solution composition, carbon dioxide absorption capacity, pH>At 9.4, the crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S; when the pH is 8.3-9.4, continuously introducing carbon dioxide, wherein the crystalline solid is a mixture of sodium carbonate and sodium bicarbonate; when PH =8.3, the crystalline solid is sodium bicarbonate and the solution no longer has the capacity to absorb carbon dioxide; after the solid-liquid mixture after absorbing the carbon dioxide passes through liquid-solid separation equipment, the slurry with high solid content is transferred into a sodium carbonate or sodium bicarbonate treatment unit; returning the clear liquid with low solid content after liquid-solid separation to the step 3 to supplement sodium sulfide and process condensate water to prepare an absorbent solution; the produced hydrogen sulfide gas is sent to a hydrogen sulfide treatment unit.
6. Packaging sodium carbonate or bicarbonate product: the slurry separated in the step 5 is dried and then respectively packaged according to the product components
Assembling; the solid separated from the liquid and the solid becomes a sodium bicarbonate product after being dried, and the process water evaporated by drying can be sent into a sodium sulfide absorption carbon dioxide unit to prepare a sodium sulfide solution; and (3) further decomposing the sodium bicarbonate to generate sodium carbonate and carbon dioxide, wherein the sodium carbonate can be used as a product for packaging, and the generated carbon dioxide is collected and then sent to the step (4) to be used as a raw material gas.
7. Hydrogen sulfide and oxygen combustion reaction: hydrogen sulfide separated out from carbon dioxide absorption unit by sodium sulfide and mixed gas after washing
In order to prevent the hydrogen sulfide-rich mixed gas from forming an explosive mixture with oxygen, the oxygen content of the raw material mixed gas entering the sodium sulfide absorption carbon dioxide unit should be less than 4%. Pumping the separated sulfur-containing gas to a hydrogen sulfide gas collecting tank or a gas holder, and then sending the gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is in thermal combination with the sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reducing gas and the sodium sulfate solid in the sodium sulfate reduction unit. The sulfuric acid obtained in the step can be used as a final product for product packaging.
8. Hydrogen sulfide electrolysis reaction: the hydrogen sulfide in the step 8 is sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide; the sulfur produced by indirect electrolysis can be used as a final product for product packaging.
9. Preparing hydrochloric acid by using sulfuric acid: and (3) taking industrial sodium chloride and the sulfuric acid produced in the step (7) as raw materials, producing sodium sulfate and hydrogen chloride gas, absorbing the hydrogen chloride gas to prepare hydrochloric acid solution, crystallizing and drying the sodium sulfate, and then sending the sodium sulfate to a sodium sulfate reduction unit. And packaging the obtained hydrochloric acid serving as a final product.
Example 2
Referring to fig. 5 and fig. 20, in this example, sodium sulfate is used as a raw material, hydrogen is produced by electrolyzing water, and after absorbing carbon dioxide,
sodium bicarbonate and sulfuric acid were produced in the same manner as in example 1 except for the following points:
1. the oxygen produced in step 1 is sent to a sulfuric acid device of a hydrogen sulfide treatment unit through an output pipeline.
2. And 3, adding sodium sulfide into the solution preparation equipment in a concentration solution supplementing manner. Step 3, the temperature of the absorbent is 45 ℃; the concentration of sodium sulfide and the concentration of sodium carbonate are determined according to the concentration of carbon dioxide and the oxygen content in the feed gas: in the absorbent solution, the content of sodium sulfide in each 100g of water is 0.6mol, the content of sodium carbonate in each 100g of water is 0.3mol, and the operating pressure of a carbon dioxide absorption unit is 3MPa.
3. Step 4, see fig. 20. Since the present embodiment provides two carbon dioxide absorption towers, the carbon dioxide absorption tower vent gas in the former item is connected to another group of carbon dioxide absorption towers as the latter item through the output line, instead of being connected to the hydrogen sulfide treatment unit. Two sodium sulfide solution absorption carbon dioxide units are subjected to gas-liquid phase series-parallel coupling combination, the exhaust gas of the former carbon dioxide absorption tower is connected with a feed gas inlet conveyed to the latter carbon dioxide absorption tower through an output pipeline, and the clear liquid discharged by the latter liquid-solid separation equipment is conveyed to a feed material inlet of the former solution preparation equipment. The exhaust gas of the carbon dioxide absorption tower is provided with a demister and a cooler.
4. In the step 7, the hydrogen sulfide is sent to a subsequent sulfuric acid device, and when the process water for producing the sulfuric acid solution is insufficient, the hydrogen sulfide needs to be supplemented in time.
5. In the embodiment, the combination of more than two units for absorbing carbon dioxide can timely take the precipitated sodium carbonate or sodium bicarbonate out of the system, and separate absorption working conditions of two different absorbents, namely carbon dioxide absorbed by sodium sulfide washing and carbon dioxide absorbed by sodium carbonate washing, are operated; the combination of more than two units for absorbing carbon dioxide ensures that the system is more flexible in adjusting temperature, concentration, heat removal, solid content discharge and the like, and improves the utilization rate of sodium sulfide; when the absorption tower/reactor combined type hydrogen sulfide absorption tower/hydrogen carbonate generator works, water is supplemented to each group of absorption tower/reactor for cooling, the solid content is reduced through water supplement, and the water consumption during generation of hydrogen sulfide and sodium bicarbonate is compensated through water supplement.
Example 3
Referring to fig. 6, the present embodiment is a method for producing hydrogen from electrolyzed water by using sodium sulfate as a raw material, and producing sodium bicarbonate, sulfur and pure oxygen after absorbing carbon dioxide, and the steps are the same as those in embodiment 1 except for the following points:
1. taking oxygen as a final product in the step 1;
2. and 3, adding the sodium sulfide into the solution preparation equipment in a concentration solution supplementing mode. Step 3, the temperature of the absorbent is 30 ℃; the concentration of sodium sulfide and the concentration of sodium carbonate are determined according to the concentration of carbon dioxide and the oxygen content in the feed gas: in the absorbent solution, the content of sodium sulfide in each 100g of water is 0.7mol, the content of sodium carbonate in each 100g of water is 0, and the operating pressure of a carbon dioxide absorption unit is 1MPa; .
3. And 8, sending the hydrogen sulfide to a subsequent indirect hydrogen sulfide electrolysis device, wherein the electrolysis device does not generate heat any more, the heat of the sodium sulfate reduction unit needs to be additionally increased, and hydrogen generated by the hydrogen sulfide electrolysis device is sent to the sodium sulfate reduction unit for recycling.
Example 4
Referring to fig. 7, the present example is a method for producing sodium bicarbonate and sulfuric acid by using sodium sulfate as a raw material and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those of example 1 except that:
1. in the step 1, oxygen is sent to a sulfuric acid device, and the residual oxygen is used as a final product;
2. and 3, adding the sodium sulfide into the solution preparation equipment in a concentration solution supplementing mode. Step 3, the temperature of the absorbent is 80 ℃; the concentration of sodium sulfide and the concentration of sodium carbonate are determined according to the concentration of carbon dioxide and the oxygen content in the feed gas: in the absorbent solution, the content of sodium sulfide in each 100g of water is 0, and the content of sodium carbonate in each 100g of water is 0.4mol.
3. The sulfur product generated by electrolysis is sent to a sulfuric acid device, the sulfur of the device can be prepared into pure oxygen for combustion and is thermally combined with a sodium sulfate reduction unit, and the heat generated by the combustion of hydrogen sulfide is used for heating the reduction gas and the sodium sulfate solid.
Example 5
Referring to fig. 8, the embodiment of the present invention is a method for producing sodium carbonate and sulfur products by using sodium sulfate as a raw material and by using electrolyzed water to produce hydrogen and absorbing carbon dioxide, and the method comprises the following steps:
1. the electric power output by photovoltaic power generation, wind power generation or nuclear power generation equipment or the electric power output by coal-fired power generation and a power grid system is electrolyzed into hydrogen by a water electrolysis device. In order to stabilize the source of hydrogen, fossil energy or biomass hydrogen production and synthesis gas devices can be prepared to supplement reducing gas, and in the reducing gas components, the content except hydrogen is as small as possible, the hydrogen or the reducing gas is sent to a sodium sulfate reduction unit, and oxygen is sent to a sulfur recovery unit; if the hydrogen supply unit does not supply hydrogen by electrolyzed water, hydrogen is produced by fossil energy or biomass, and if the components of the hydrogen supply unit contain carbon monoxide, carbon dioxide or methane components,
in the reaction tail gas of reducing sodium sulfate, carbon dioxide in the tail gas can be removed by using a sodium sulfide solution, and simultaneously a sodium carbonate or sodium bicarbonate product is produced;
2. hydrogen enters a sodium sulfate reduction unit, sodium sulfate raw materials are reduced into sodium sulfide products at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously carried out, and simultaneously, process condensate water and the temperature of sodium sulfide solid products are produced
The temperature can be controlled to be about 100 ℃, and the temperature of the process water can be controlled to be about 90 ℃, so that the temperature and the process water can be prepared into a high-concentration sodium sulfide solution, and meanwhile, the dissolving and heating energy sources are saved; the produced process water can be sent to the water electrolysis hydrogen production unit after being treated by the reverse osmosis membrane.
3. The sodium sulfide product is sent to a solution preparation unit to form a high-temperature high-concentration sodium sulfide solution, in order to accelerate the dissolution of sodium sulfide, the absorption of carbon dioxide and the desorption of hydrogen sulfide, the solution preparation can be carried out in a container with a slight stirring device, the sodium sulfide solution can be prepared into a concentrated solution with the temperature of about 90 ℃, and the mass of the sodium sulfide in 100g of water of the solution is less than 0.77 time of the solubility at the temperature.
4. Flue gas discharged by a coal-fired boiler or enriched carbon dioxide gas is introduced into a sodium sulfide solution, and equipment for absorbing carbon dioxide and desorbing hydrogen sulfide can be a container or a reaction kettle with slight stirring or an absorption tower with a solid-phase discharging function. The higher the carbon dioxide concentration in the raw material gas is, the lower the oxygen content is, the higher the concentration of sodium sulfide in the absorbent solution is, and the lower the concentration of sodium carbonate is; the lower the carbon dioxide concentration in the feed gas, the higher the oxygen content, and the lower the sodium sulfide concentration in the absorbent solution, the higher the sodium carbonate concentration.
5. The amount of carbon dioxide added is adjusted according to the pH of the solution, when the pH is not lower than>At 9.4, the anion in the solution is S 2- 、HS - 、CO 3 2- And OH - Ion, no HCO in solution 3 - Ionic, crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S, stopping introducing carbon dioxide, and transferring the solid-liquid product to a sodium carbonate treatment unit; in order to enhance the carbon dioxide absorption effect, the present embodiment is configured as a plurality of carbon dioxide absorption towers, absorption tanks or stirred tanks, and the following steps are divided according to the working state and are performed in a circulating manner:
(1) Preparing a sodium sulfide solution with proper concentration, wherein the mass of sodium sulfide in 100g of water in the solution is less than 0.77 times of the solubility of sodium sulfide at the temperature;
(2) Introducing carbon dioxide to precipitate and discharge hydrogen sulfide gas, sending the produced gas to a hydrogen sulfide treatment unit, stopping sending the produced gas to the hydrogen sulfide treatment unit when the pH of the solution is more than or equal to 9.4, stopping introducing the carbon dioxide, and transferring the solution to standing and liquid-solid separation equipment for treatment;
(3) And (4) returning the mother liquor after liquid-solid separation to the step (1), supplementing sodium sulfide and process condensate water, and repeating the step (1).
The separated hydrogen sulfide and the washed mixed gas form sulfur-containing gas which is the raw material gas of the hydrogen sulfide processing unit, and in order to avoid the hydrogen sulfide-rich mixed gas and oxygen forming an explosive mixture, the oxygen content of the raw material mixed gas entering the sodium sulfide unit for absorbing carbon dioxide is less than 4%. Pumping the separated sulfur-containing gas to a hydrogen sulfide gas collecting tank or a gas holder, and then sending the gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is in thermal combination with the sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reducing gas and the sodium sulfate solid in the sodium sulfate reduction unit.
6. 5, drying the solid separated from gas-solid, and packaging the product by taking the product component as sodium carbonate;
7. hydrogen sulfide and oxygen combustion reaction: the sodium sulfide absorbs the hydrogen sulfide-containing gas discharged from the carbon dioxide unit, and the hydrogen sulfide-containing gas and the oxygen prepared by the hydrogen supply unit are combusted and oxidized to prepare sulfuric acid products, the sulfuric acid is put into the sulfuric acid-making hydrochloric acid unit, meanwhile, the heat produced by the combustion of the hydrogen sulfide is used for heating and warming the reducing gas and the sodium sulfate solid of the sodium sulfate reducing unit, and the discharged gas after desulfurization treatment is qualified
And is discharged to the atmosphere.
Hydrogen sulfide electrolysis reaction: the hydrogen sulfide in the step 7 can also be sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide.
Example 6
Referring to fig. 9, the present example is a method for producing sodium carbonate and sulfuric acid products by using sodium sulfate as a raw material and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those in example 5 except for the following points:
1. in the step 1, the produced oxygen is sent to a sulfuric acid device;
2. in step 6, the hydrogen sulfide is sent to a subsequent sulfuric acid plant.
Example 7
Referring to fig. 10, the present example is a method for producing sodium carbonate and sulfur products by using sodium sulfate as a raw material and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those in example 5 except that:
1. taking oxygen as a final product in the step 1;
2. in step 7, the hydrogen sulfide is sent to a subsequent indirect hydrogen sulfide electrolysis device, the electrolysis device does not generate heat any more, and the sodium sulfate is also used for electrolysis
The heat of the original unit needs to be additionally increased.
Example 8
Referring to fig. 11, this example is a method for producing sodium carbonate and sulfuric acid products by using sodium sulfate as a raw material and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those of example 7 except that:
1. in the step 1, oxygen is sent to a sulfuric acid device, and a part of oxygen which is surplus is used as a final product;
2. the sulfur product generated by electrolysis is sent to a sulfuric acid device, the sulfur of the device can be prepared into pure oxygen for combustion, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of hydrogen sulfide is used for heating reducing gas and sodium sulfate solid.
Example 9
Referring to fig. 12, in this embodiment, the method for producing hydrogen by electrolyzing water and absorbing carbon dioxide by using sodium sulfate and sodium chloride as raw materials to produce sodium bicarbonate, sulfur, sulfuric acid and hydrochloric acid includes the following steps:
1. the electric power output by photovoltaic power generation, wind power generation or nuclear power generation equipment or the electric power output by coal-fired power generation and a power grid system is electrolyzed into hydrogen by a water electrolysis device. In order to stabilize the hydrogen source, a fossil energy or biomass hydrogen production and synthesis gas device can be prepared to supplement reducing gas, the content of the reducing gas component except hydrogen is less and better, the hydrogen or the reducing gas is sent to a sodium sulfate reduction unit, and oxygen is sent to a sulfur device and a sulfuric acid device;
2. hydrogen enters a sodium sulfate reduction unit, sodium sulfate raw materials are reduced into sodium sulfide products at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously carried out, and meanwhile, process condensate water is produced, the temperature of a sodium sulfide solid product can be controlled to be about 100 ℃, and the temperature of the process water can be controlled to be about 90 ℃, so that the sodium sulfide solid product and the process water are prepared into a high-concentration sodium sulfide solution, and meanwhile, the dissolving and heating energy is saved;
3. the sodium sulfide product is sent to a solution preparation unit to form a high-temperature high-concentration sodium sulfide solution, in order to accelerate the dissolution of sodium sulfide, the absorption of carbon dioxide and the desorption of hydrogen sulfide, the solution preparation can be carried out in a container with a slight stirring device, the sodium sulfide solution can be prepared into a concentrated solution at about 90 ℃, and the mass of the sodium sulfide in 100g of water of the solution is less than 0.77 time of the solubility at the temperature;
4. flue gas discharged by a coal-fired boiler or enriched carbon dioxide gas is introduced into a sodium sulfide solution, and equipment for absorbing carbon dioxide and desorbing hydrogen sulfide can be a container or a reaction kettle with slight stirring or an absorption tower with a solid-phase discharging function, and the equipment has strong acid and alkali resistance;
5. the amount of carbon dioxide added is adjusted according to the pH of the solution, when the pH is>At 9.4, the anion in the solution is S 2- 、HS - 、CO 3 2- And OH - Ion, no HCO in solution 3 - Ionic, crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S; when the PH value is 8.3 to 9.4, carbon dioxide is continuously introduced to the solution
The ions mainly consisting of CO 3 2- And HCO 3 - The particles being formed by a mixture of sodium carbonate and sodium bicarbonate as crystalline solidA compound; when pH =8.3, there was no CO in the solution anions 3 2- The ion, crystalline solid is sodium bicarbonate, the solution no longer absorbs carbon dioxide, the introduction of carbon dioxide is stopped, and the solid-liquid product is transferred to a sodium carbonate or sodium bicarbonate treatment unit. Can be arranged into a plurality of carbon dioxide absorption towers, absorption tanks or stirred tanks, and is divided into the following steps according to the working state and circularly carried out:
(1) Preparing a sodium sulfide solution with proper concentration, wherein the mass of sodium sulfide in 100g of water in the solution is less than 0.77 time of the solubility of the sodium sulfide at the temperature;
(2) Introducing carbon dioxide for precipitation and discharging hydrogen sulfide gas, sending the produced gas to a hydrogen sulfide treatment unit, and stopping sending the produced gas to the hydrogen sulfide treatment unit when the pH of the solution is more than or equal to 9.4; if the required product is sodium carbonate, stopping introducing the carbon dioxide, and transferring to standing and liquid-solid separation equipment for treatment; in the embodiment, when the pH =9.4, the produced gas is stopped from being sent to the hydrogen sulfide treatment unit, but carbon dioxide is continuously introduced;
(3) The pH value of the solution is more than 8.3 and less than 9.4, the carbon dioxide is introduced to not separate out hydrogen sulfide, and the produced gas is sent to a tail gas treatment unit
Absorbing acid gas with sodium hydroxide, discharging into atmosphere, and producing sodium bicarbonate ion and sodium bicarbonate crystal solid in the solution
Precipitating;
(4) Stopping introducing carbon dioxide when the pH value of the solution is =8.3, and transferring the solution to a standing and liquid-solid separation device for treatment;
(5) And (4) returning the mother liquor after liquid-solid separation to the step (1), supplementing sodium sulfide and process condensate water, and repeating the step (1).
6. The separated hydrogen sulfide and the washed mixed gas form sulfur-containing gas, the sulfur-containing gas is raw material gas of the hydrogen sulfide processing unit, and in order to avoid explosive mixture formed by the hydrogen sulfide-rich mixed gas and oxygen, the oxygen content of the raw material mixed gas entering the sodium sulfide carbon dioxide absorption unit is less than 4%. Pumping the separated sulfur-containing gas to a hydrogen sulfide gas collecting tank or a gas holder, and then sending the gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reduction gas and the sodium sulfate solid in the sodium sulfate reduction unit; and (3) drying the solid separated from gas and solid, packaging the product according to the product components of the solid as sodium bicarbonate, and sending the evaporated process water into a sodium sulfide absorption carbon dioxide unit to prepare a sodium sulfide solution.
7. Hydrogen sulfide and oxygen combustion reaction: the method comprises the following steps that sodium sulfide absorbs hydrogen sulfide-containing gas discharged from a carbon dioxide unit, the hydrogen sulfide-containing gas and oxygen prepared by a hydrogen supply unit are combusted and oxidized to prepare a sulfuric acid product, sulfuric acid is put into a sulfuric acid-hydrochloric acid preparation unit, the principle that volatile acid gas is prepared by using hard-volatile acid is utilized, sulfuric acid and sodium chloride are mixed in a reactor to analyze hydrogen chloride gas, a dilute hydrochloric acid solution is used for absorbing the volatilized hydrogen chloride gas, sodium sulfate crystals are obtained at the same time, and water in the mixed reactor needs to be supplemented in time when insufficient water exists; meanwhile, the heat produced by burning the hydrogen sulfide is used for heating the reducing gas and the sodium sulfate solid in the sodium sulfate reduction unit, and the exhaust gas after desulfurization is discharged into the atmosphere after being qualified.
8. Hydrogen sulfide electrolysis reaction: the hydrogen sulfide in the step 7 can also be sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide.
9. Preparing hydrochloric acid by using sulfuric acid: industrial sodium chloride and sulfuric acid are used as raw materials, sodium sulfate and hydrogen chloride gas are produced, the hydrogen chloride gas is absorbed to prepare hydrochloric acid solution, and the sodium sulfate is crystallized and dried and then is sent to a sodium sulfate reduction unit.
Example 10
Referring to fig. 13, this example is a method for producing sodium bicarbonate, sulfuric acid and hydrochloric acid by using sodium sulfate and sodium chloride as raw materials and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those of example 9 except for the following points:
1. step 1 is changed as follows: the electric power output by photovoltaic power generation, wind power generation or nuclear power generation equipment or the electric power output by coal-fired power generation and a power grid system is electrolyzed into hydrogen by the water electrolysis device. In order to stabilize the hydrogen source, a fossil energy or biomass hydrogen production and synthesis gas device can be prepared to supplement reducing gas, the content of the reducing gas components except hydrogen is as small as possible, the hydrogen or the reducing gas is sent to a sodium sulfate reduction unit, and oxygen is sent to a sulfuric acid device;
2. step 7 is changed as follows: pumping the separated hydrogen sulfide gas to a hydrogen sulfide gas-collecting tank or a gas holder, and sending the hydrogen sulfide gas to a subsequent sulfuric acid device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating reducing gas and sodium sulfate solid; when the process water of the sulfuric acid device is insufficient, the process water needs to be supplemented in time.
Example 11
Referring to fig. 14, the present example is a method for producing hydrogen from electrolyzed water by using sodium sulfate and sodium chloride as raw materials, and producing sodium bicarbonate, sulfur, sulfuric acid and hydrochloric acid after absorbing carbon dioxide, and the steps thereof are the same as those in example 9 except for the following points:
and 8, sending the hydrogen sulfide to a subsequent indirect hydrogen sulfide electrolysis device, wherein the electrolysis device does not generate heat any more, the heat of the sodium sulfate reduction unit needs to be additionally increased, and hydrogen generated by the hydrogen sulfide electrolysis device is sent to the sodium sulfate reduction unit for recycling.
Example 12
Referring to fig. 15, the present embodiment is a method for producing sodium carbonate, sulfur, sulfuric acid and hydrochloric acid by using sodium sulfate and sodium chloride as raw materials and using electrolyzed water to produce hydrogen and absorbing carbon dioxide, and the method comprises the following steps:
1. the electric power output by photovoltaic power generation, wind power generation or nuclear power generation equipment or the electric power output by coal-fired power generation and a power grid system is electrolyzed into hydrogen by a water electrolysis device. In order to stabilize the hydrogen source, a fossil energy source or a biomass hydrogen production and synthesis gas device can be prepared to supplement reducing gas, and the reducing gas component has the content except hydrogen as less as possible, so that the hydrogen is added
The gas or reducing gas is sent to a sodium sulfate reducing unit, and the oxygen is sent to a sulfur recovery unit.
2. Hydrogen enters a sodium sulfate reduction unit, a sodium sulfate raw material is reduced into a sodium sulfide product at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously carried out, and simultaneously, process condensate water is produced, the temperature of a sodium sulfide solid product can be controlled at 100 ℃, the temperature of the process water can be controlled at 90 ℃, so that the sodium sulfide solid product and the process water are prepared into a high-concentration sodium sulfide solution, and meanwhile, the dissolving and heating energy is saved.
3. The sodium sulfide product is sent to a solution preparation unit to form a high-temperature high-concentration sodium sulfide solution, in order to accelerate the dissolution of sodium sulfide, the absorption of carbon dioxide and the desorption of hydrogen sulfide, the solution preparation can be carried out in a container with a slight stirring device, the sodium sulfide solution can be prepared into a concentrated solution with the temperature of about 90 ℃, and the mass of the sodium sulfide in 100g of water of the solution is less than 0.77 time of the solubility at the temperature;
4. flue gas discharged by a coal-fired boiler or enriched carbon dioxide gas is introduced into a sodium sulfide solution, and equipment for absorbing carbon dioxide and desorbing hydrogen sulfide can be a container or a reaction kettle with slight stirring or an absorption tower with a solid-phase discharging function, and the equipment has strong acid and alkali resistance;
5. the amount of carbon dioxide added is adjusted according to the pH of the solution, when the pH is not lower than>At 9.4, the anion in the solution is S 2- 、HS - 、CO 3 2- And OH - Ion, no HCO in solution 3 - Ionic, crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S, stopping introducing carbon dioxide, and transferring the solid-liquid product to a sodium carbonate treatment unit; the method is characterized in that the method is provided with a plurality of carbon dioxide absorption towers, absorption tanks or stirred tanks, and comprises the following steps according to the working state and is carried out in a circulating mode:
(1) Preparing a sodium sulfide solution with proper concentration, wherein the mass of sodium sulfide in 100g of water in the solution is less than 0.77 times of the solubility of sodium sulfide at the temperature;
(2) Introducing carbon dioxide to precipitate and discharge hydrogen sulfide gas, sending the produced gas to a hydrogen sulfide treatment unit, stopping sending the produced gas to the hydrogen sulfide treatment unit when the pH of the solution is more than or equal to 9.4, stopping introducing the carbon dioxide, and transferring the solution to standing and liquid-solid separation equipment for treatment;
(3) Returning the mother liquor after liquid-solid separation to the step (1), supplementing sodium sulfide and process condensate water, and repeating the step (1);
6. the separated hydrogen sulfide and the washed mixed gas form sulfur-containing gas, the sulfur-containing gas is raw material gas of the hydrogen sulfide processing unit, and in order to avoid explosive mixture formed by the hydrogen sulfide-rich mixed gas and oxygen, the oxygen content of the raw material mixed gas entering the sodium sulfide carbon dioxide absorption unit is less than 4%. Pumping the separated sulfur-containing gas to a hydrogen sulfide gas collecting tank or a gas holder, and then sending the gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reduction gas and the sodium sulfate solid in the sodium sulfate reduction unit; packaging sodium carbonate or bicarbonate product: drying the slurry separated in the step (5), and then respectively packaging the dried slurry according to the product components; sodium carbonate and carbon dioxide are generated after sodium bicarbonate is decomposed, the sodium carbonate is used as a product for packaging, and the generated carbon dioxide is collected and then sent to the step (4) to be used as raw material gas.
7. The separated hydrogen sulfide and the washed mixed gas form sulfur-containing gas which is the raw material gas of the hydrogen sulfide processing unit, and in order to avoid the hydrogen sulfide-rich mixed gas and oxygen forming an explosive mixture, the oxygen content of the raw material mixed gas entering the sodium sulfide unit for absorbing carbon dioxide is less than 4%. Pumping the separated sulfur-containing gas to a hydrogen sulfide gas collecting tank or a gas holder, and then sending the gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reduction gas and the sodium sulfate solid in the sodium sulfate reduction unit; separating the solid from the gas, drying
And then the product is packaged by taking the product components as sodium carbonate.
8. Hydrogen sulfide electrolysis reaction: the hydrogen sulfide generated in the step 7 can also be sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide.
9. And 7, conveying the sulfuric acid produced in the step 7 to a sodium chloride hydrochloric acid preparation device, mixing the sulfuric acid and sodium chloride in a reactor to analyze hydrogen chloride gas by utilizing the principle of preparing volatile acidic gas by using difficult-to-volatile acid, absorbing the volatilized hydrogen chloride gas by using a dilute hydrochloric acid solution, and simultaneously obtaining sodium sulfate crystals, wherein the sodium sulfate crystals are required to be supplemented in time when the water in the mixing reactor is insufficient.
Example 13
Referring to fig. 16, the present example is a method for producing sodium carbonate, sulfuric acid and hydrochloric acid by using sodium sulfate and sodium chloride as raw materials and electrolyzing water, and absorbing carbon dioxide, and the steps are the same as those of example 12 except that:
1. step 1 is changed into: electric power output from photovoltaic, wind or nuclear power plants, or coal-fired power generation and
the power output by the power grid system is electrolyzed into hydrogen by the water electrolysis device. In order to stabilize the hydrogen source, a fossil energy or biomass hydrogen production and synthesis gas device can be prepared to supplement reducing gas, the content of the reducing gas components except hydrogen is as small as possible, the hydrogen or the reducing gas is sent to a sodium sulfate reduction unit, and oxygen is sent to a sulfuric acid device.
2. Step 7 is changed as follows: pumping the separated hydrogen sulfide gas to a hydrogen sulfide gas collecting tank or a gas holder, and sending the hydrogen sulfide gas to subsequent sulfuric acid filling
And (4) placing. The device can prepare pure oxygen for combustion by hydrogen sulfide, and is thermally combined with a sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating reducing gas and sodium sulfate solid; when the process water of the sulfuric acid device is insufficient, the process water is supplemented in time.
Example 14
Referring to fig. 17, the present example is a method for producing sodium carbonate, sulfur, sulfuric acid, and hydrochloric acid by using sodium sulfate and sodium chloride as raw materials and electrolyzing water to produce hydrogen and absorbing carbon dioxide, and the steps are the same as those in example 12 except for the following points:
in the step 7, the hydrogen sulfide is sent to a subsequent indirect hydrogen sulfide electrolysis device or a sulfuric acid device; the heat generated by the sulfuric acid device can be used for heating up with the raw materials in the sodium sulfate reduction unit, and the hydrogen generated by the hydrogen sulfide electrolysis device is sent to the sodium sulfate reduction unit for recycling.
Example 15
Referring to fig. 18, the carbon dioxide containing feed gas in this example had an oxygen content greater than 4.3%, and if treated according to any of the embodiments 1-14, an explosive mixture of hydrogen sulfide would form in the hydrogen sulfide rich decarbonized gas, which would be dangerous when encountering an ignition source. To avoid formation of explosive mixtures, this example was modified as shown in fig. 18. In the embodiment, sodium sulfate is used as a raw material, hydrogen is produced by electrolyzing water, the sodium sulfate is reduced by hydrogen to obtain sodium sulfide, sulfuric acid produced by a hydrogen sulfide treatment unit reacts with sodium chloride to obtain sodium sulfate and hydrochloric acid, and the sodium sulfate can be continuously used as the raw material to produce the sodium sulfide. The difference from examples 1 to 14 is that in this example, the carbon dioxide-containing feed gas is not directly introduced into the sodium sulfide solution, but is introduced into the sodium carbonate solution formed by the absorption of carbon dioxide by sodium sulfide, and the carbon dioxide absorbed by sodium sulfide is derived from the carbon dioxide generated by the thermal decomposition of sodium bicarbonate. Which comprises the following steps:
1. the electric power output by photovoltaic power generation, wind power generation or nuclear power generation equipment or the electric power output by coal-fired power generation and a power grid system is electrolyzed into hydrogen by a water electrolysis device. In order to stabilize the hydrogen source, a fossil energy or biomass hydrogen production and synthesis gas device can be configured to supplement reducing gas, and the content of the reducing gas components except hydrogen is preferably less. Hydrogen or fossil energy reducing gas generated by electrolysis is sent to a sodium sulfate reduction unit, partial oxygen generated by electrolysis is sent to a sulfur recovery unit, and the rest oxygen can be used as an oxygen product.
2. Hydrogen enters a sodium sulfate reduction unit, a sodium sulfate raw material is reduced into a sodium sulfide product at high temperature, wherein the feeding of sodium sulfate and hydrogen and the discharging of sodium sulfide can be continuously carried out, process condensate water is produced simultaneously, the temperature of a produced sodium sulfide solid product is controlled to be about 100 ℃, and the temperature of the produced process water is controlled to be about 90 ℃, so that the sodium sulfide solid product and the sodium sulfide solid product are prepared into a high-concentration sodium sulfide solution, and meanwhile, the dissolving and heating energy sources are saved.
3. The sodium sulfide product and the process water are sent to a solution preparation unit to form a high-temperature high-concentration sodium sulfide solution, the solution preparation can be carried out in a container with a slight stirring device for accelerating the dissolution of sodium sulfide, the absorption of carbon dioxide and the desorption of hydrogen sulfide, the sodium sulfide solution can be prepared into a concentrated solution at about 90 ℃, and the mass of the sodium sulfide in 100g of solution water is less than 0.77 time of the solubility of the sodium sulfide at the temperature.
4. Carbon dioxide generated by thermal decomposition of sodium bicarbonate is introduced into the sodium sulfide solution, and hydrogen sulfide gas is separated out at the same time. The amount of carbon dioxide added was adjusted according to the pH of the solution. When the pH is higher>At 9.4, the anion in the solution is S 2- 、HS - 、CO 3 2- And OH - Ion, no HCO in solution 3 - Ionic, crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 And S, stopping introducing carbon dioxide and simultaneously stopping exhausting hydrogen sulfide gas. At PH =9.4 the solution and precipitate were essentially sodium carbonate, and after stopping carbon dioxide feed and hydrogen sulfide removal, the resulting solution and solids were transferred to step 5 as a solution for absorbing carbon dioxide in the feed gas.
The carbon dioxide-containing feed gas with the oxygen content of more than 4.3 percent is introduced into the sodium carbonate solution, and the equipment for absorbing the carbon dioxide can be a container or a reaction kettle with slight stirring or an absorption tower with a solid phase discharging function, and the equipment has strong acid and alkali resistance. Meanwhile, the raw material gas is directly discharged to the atmosphere after being washed to absorb carbon dioxide.
5. The PH of the solution is continuously reduced along with the introduction of the raw material gas, and the anion of the solution is mainly composed of CO 3 2- And HCO 3 - Particle composition, the crystalline solid being a mixture of sodium carbonate and sodium bicarbonate; when pH =8.3, there was no CO in the solution anions 3 2- And (3) the ions and the crystalline solid are sodium bicarbonate, the solution does not absorb carbon dioxide any more, the introduction of carbon dioxide is stopped, the discharge of decarbonized gas is stopped, and the liquid-solid product is transferred to a sodium bicarbonate separation and precipitation separation unit.
6. After the liquid-solid product is subjected to standing, precipitation and separation, the mother liquor is a sodium bicarbonate solution and is sent to a sodium sulfide preparation unit to prepare a sodium sulfide absorption liquid again; the solid precipitate goes to the drying and sodium bicarbonate thermal decomposition steps. After the decomposed carbon dioxide and water vapor are cooled and dehydrated, the gas is sent to a sodium sulfide absorption unit to be used as a solution, and condensed water can be supplemented to other water using places for use.
7. Pumping the separated hydrogen sulfide gas to a hydrogen sulfide gas collecting tank or a gas holder, and then conveying the hydrogen sulfide gas to a subsequent sulfur device; the device can prepare pure oxygen for combustion by hydrogen sulfide, and is in thermal combination with the sodium sulfate reduction unit, and the heat generated by combustion of the hydrogen sulfide is used for heating the reducing gas and the sodium sulfate solid in the sodium sulfate reduction unit.
8. Hydrogen sulfide electrolysis reaction: the hydrogen sulfide in the step 7 can also be sent to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and the hydrogen can be sent to a sodium sulfate reduction unit for producing sodium sulfide.
In this embodiment, the process water produced in step 2 can be sent to a process for preparing hydrogen or sodium sulfide solution by electrolyzing water after being treated by a reverse osmosis membrane. If the hydrogen supply unit in the step 1 does not supply hydrogen by electrolyzed water, hydrogen is produced and supplied by fossil energy or biomass, reducing gas components of the hydrogen supply unit contain carbon monoxide, carbon dioxide or methane components, and in reaction tail gas of reducing sodium sulfate, a sodium sulfide solution can be used for removing the carbon dioxide in the tail gas and simultaneously producing sodium carbonate or sodium bicarbonate products. The steps 4, 5 and 6 can be set into a plurality of sodium sulfide solution preparation tanks, an absorption tower, an absorption tank or a stirring kettle for absorbing carbon dioxide by sodium sulfide, an absorption tower, an absorption tank or a stirring kettle for absorbing feed gas by sodium carbonate, liquid-solid separation equipment and solid phase drying and thermal decomposition equipment, and are circularly carried out step by step according to the working state.

Claims (12)

1. An industrial carbon sequestration system that absorbs carbon dioxide gas which characterized in that: the system comprises a hydrogen supply unit, a sodium sulfate reduction unit, a sodium sulfide solution absorption carbon dioxide unit, a sodium carbonate treatment unit and a hydrogen sulfide treatment unit;
the hydrogen produced by the hydrogen supply unit is connected with the sodium sulfate reduction unit through an output pipeline;
the sodium sulfate reduction unit reduces sodium sulfate into sodium sulfide by hydrogen, the produced sodium sulfide is sent to a sodium sulfide solution absorption carbon dioxide unit, and the produced sodium sulfide is sent to a sodium sulfide solution absorption carbon dioxide unit; the produced water is sent to other units to be used as water supplement;
the unit for absorbing carbon dioxide by the sodium sulfide solution comprises absorbent solution preparation equipment, a carbon dioxide absorption tower/reactor, liquid-solid separation equipment, a slurry discharge pump and a solution circulating pump; the outlet of the carbon dioxide-containing raw material gas storage device is connected with a raw material gas inlet at the bottom of a carbon dioxide absorption tower/reactor, the exhaust gas of the carbon dioxide absorption tower/reactor is connected with a hydrogen sulfide treatment unit or another group of carbon dioxide absorption tower/reactor through an output pipeline, a slurry outlet at the bottom of the carbon dioxide absorption tower/reactor is connected with a raw material inlet of a liquid-solid separation device through a pipeline, a clear liquid outlet of the liquid-solid separation device is connected with an inlet of a solution circulating pump through a pipeline, a slurry outlet of the liquid-solid separation device is connected with a raw material inlet of a sodium carbonate treatment unit through a slurry discharge pump, an outlet of the solution circulating pump is connected with a raw material inlet of a solution preparation device through a pipeline, the exhaust gas of the solution preparation device is connected with the raw material gas inlet of the hydrogen sulfide treatment unit through a pipeline, sodium sulfide is injected into an absorbent solution preparation device through a pipeline, a liquid outlet of the solution preparation device is connected with a liquid inlet at the upper part of the carbon dioxide absorption tower/reactor through an output pipeline, and deionized water pipelines are arranged at the middle parts of the carbon dioxide absorption tower/reactor and the solution preparation device;
the sodium carbonate processing unit is provided with sodium carbonate/sodium bicarbonate slurry processing equipment, the slurry discharged by the liquid-solid separation equipment through the slurry discharge pump is crystallized, dried or decomposed, the produced liquid-phase material and gas-phase material are respectively sent to the sodium sulfide solution absorption carbon dioxide unit through pipelines, and the solid-phase product can be packaged as a product;
the hydrogen sulfide treatment unit comprises a sulfur preparation device and/or a sulfuric acid preparation device and/or a sodium hydroxide washing and absorbing hydrogen sulfide device, and the exhaust gas of the hydrogen sulfide treatment unit is decarburization and desulfurization exhaust gas; the sulfur preparation device converts hydrogen sulfide into a sulfur product, and the sulfuric acid preparation device combusts, oxidizes, dissolves and absorbs the hydrogen sulfide and oxygen to prepare a sulfuric acid product.
2. The industrial carbon sequestration system of claim 1, wherein: the system also comprises a sulfuric acid hydrochloric acid preparation unit, wherein the sulfuric acid hydrochloric acid preparation unit is provided with a sulfuric acid hydrochloric acid preparation device, sulfuric acid reacts with sodium chloride to produce sodium sulfate and hydrochloric acid, and the sodium sulfate crystal is dried and then returns to the sodium sulfate reduction unit for recycling.
3. The industrial carbon sequestration system of claim 1 or 2, wherein: the oxygen produced by the hydrogen supply unit is connected with the hydrogen sulfide treatment unit through an output pipeline.
4. The industrial carbon sequestration system of claim 1 or 2, wherein: the absorption tower/reactor of the unit for absorbing carbon dioxide by the sodium sulfide solution is one or more of a carbon dioxide absorption tank, a stirring kettle and a carbon dioxide absorption tower with solid phase discharge; the container for preparing the solution is provided with a mixing or stirring device; the pipeline and equipment of the unit for absorbing carbon dioxide by sodium sulfide adopt acid and alkali corrosion resistant materials or linings; a raw material gas inlet or a discharge gas outlet of the carbon dioxide absorption tower/reactor is provided with an air blower or an induced draft fan according to the requirements of the operation pressure, the processing load and the air space velocity of the absorption tower; the carbon dioxide absorption tower/reactor vent gas is provided with a demister and a cooler.
5. An industrial carbon sequestration method for absorbing carbon dioxide gas, characterized in that the industrial carbon sequestration system according to claim 1 or 3 is used, and the method comprises the following steps:
(1) Electrolyzing water to produce hydrogen: electrolyzing water into hydrogen, and sending the hydrogen to a sodium sulfate reduction unit through a pipeline;
(2) Reduction of sodium sulfate: reducing the sodium sulfate raw material into a sodium sulfide product by hydrogen at high temperature, wherein the feeding of the sodium sulfate and the hydrogen and the discharging of the sodium sulfide can be continuously operated; after the process water is treated into deionized water, the deionized water is sent to the step (1) of electrolyzing water to prepare hydrogen or the step (3) of preparing a sodium sulfide solution;
(3) Preparing an absorbent solution: in solution preparation equipment with stirring or mixing function, mixing clear liquid of liquid-solid separation equipment, deionized water and sodium sulfide to prepare an absorbent solution used by a carbon dioxide absorption tower/reactor; collecting hydrogen sulfide gas separated out during solution preparation and then sending the hydrogen sulfide gas to a hydrogen sulfide treatment unit; the prepared absorbent solution is sent into a carbon dioxide absorption tower/reactor of a sodium sulfide solution absorption carbon dioxide unit;
(4) Introducing raw gas containing carbon dioxide into the carbon dioxide absorption tower/reactor, wherein the temperature of deionized water injected into the absorbent is lower than that of the solvent; selecting absorbent solutions with different pH values and components according to the concentration of carbon dioxide and the oxygen content in the feed gas;
(5) Measuring the PH value of the solution at each part in the absorption tower/reactor in the step (4) to judge the reaction progress, the solution components and the carbon dioxide absorption capacity of each part in the absorption tower, and when the PH value is>At 9.4, the crystalline solid is sodium carbonate; when PH =9.4, S 2- The ions are nearly completely separated out, and H is not produced any more by the subsequent introduction of carbon dioxide 2 S; when the pH value is 8.3-9.4, continuously introducing carbon dioxide, wherein the crystalline solid is a mixture of sodium carbonate and sodium bicarbonate; when PH =8.3, the crystalline solid is sodium bicarbonate and the solution no longer has the capacity to absorb carbon dioxide; after the solid-liquid mixture after absorbing the carbon dioxide passes through liquid-solid separation equipment, the slurry with high solid content is transferred into a sodium carbonate or sodium bicarbonate treatment unit; returning the clear liquid with low solid phase content after liquid-solid separation to the step (3) to supplement sodium sulfide and process condensate water to prepare an absorbent solution; the produced hydrogen sulfide gas is sent to a hydrogen sulfide treatment unit;
(6) Packaging sodium carbonate or bicarbonate product: drying the slurry separated in the step (5), and then respectively packaging the dried slurry according to the product components; sodium carbonate and carbon dioxide are generated after sodium bicarbonate is decomposed, the sodium carbonate is used as a product for packaging, and the generated carbon dioxide is collected and then sent to the step (4) to be used as raw material gas;
(7) Hydrogen sulfide and oxygen combustion reaction: the sodium sulfide absorbs the hydrogen sulfide-containing gas discharged by the carbon dioxide unit, and the hydrogen sulfide-containing gas and the oxygen prepared by the hydrogen supply unit are combusted and oxidized to prepare a sulfuric acid product;
(8) Hydrogen sulfide electrolysis reaction: and (4) sending the hydrogen sulfide in the step (7) to a hydrogen sulfide indirect electrolysis device to produce sulfur and hydrogen, and sending the hydrogen to a sodium sulfate reduction unit for producing sodium sulfide.
6. The industrial carbon sequestration process of claim 5, wherein: also includes the steps of
(9) Preparing hydrochloric acid by using sulfuric acid: adding the sulfuric acid produced in the step (7) as a raw material, simultaneously using heat produced by hydrogen sulfide combustion for heating reducing gas and sodium sulfate solid in a sodium sulfate reduction unit, and discharging qualified exhaust gas after desulfurization into the atmosphere;
industrial sodium chloride and sulfuric acid are used as raw materials, sodium sulfate and hydrogen chloride gas are produced, the hydrogen chloride gas is absorbed to prepare hydrochloric acid solution, and the sodium sulfate is crystallized and dried and then is sent to a sodium sulfate reduction unit.
7. The industrial carbon sequestration process of claim 5 or 6, characterized by: and (2) conveying oxygen generated by hydrogen production through water electrolysis in the step (1) to a hydrogen sulfide treatment unit through an output pipeline.
8. The industrial carbon sequestration process of claim 5 or 6, characterized by: and (3) adopting chilling water to directly mix and cool in a sodium sulfide cooling mode in the step (2), and connecting a subsequent downstream sodium sulfide solution preparation unit.
9. The industrial carbon sequestration process of claim 5 or 6, characterized by: the temperature of the absorbent in the step (3) is 30-90 ℃; the concentration of sodium sulfide and the concentration of sodium carbonate are determined according to the concentration of carbon dioxide and the oxygen content in the feed gas: in the absorbent solution, the content of sodium sulfide in each 100g of water is 0-0.735mol, and the content of sodium carbonate in each 100g of water is 0-0.46mol; the operation temperature and the solution solid content concentration of the carbon dioxide absorption tower/reactor and the absorbent solution preparation equipment can be adjusted by adjusting the injection amount of the deionized water; the operating pressure of the carbon dioxide absorption unit is-0.1 to 3MPa.
10. The industrial carbon sequestration process of claim 5 or 6, characterized by: and (3) adding the sodium sulfide into solution preparation equipment in a mode of directly adding solids or supplementing high-concentration solution.
11. The industrial carbon sequestration process of claim 5 or 6, characterized by: in the step (4), more than two units for absorbing carbon dioxide by using sodium sulfide solution can be combined in series, and the exhaust gas of the former carbon dioxide absorption tower/reactor is connected with a raw material gas inlet conveyed to the latter carbon dioxide absorption tower/reactor through an output pipeline; a part of clear liquid discharged from the latter liquid-solid separation equipment is sent to the raw material inlet of the former solution preparation equipment.
12. The industrial carbon sequestration process of claim 5 or 6, characterized by: and (3) packaging the sulfuric acid obtained in the step (7), the sulfur produced by the step (8) through indirect electrolysis, and the hydrochloric acid obtained in the step (9) as a final product.
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