CN101979130A - Method for removing hydrogen sulfide from industrial gas in recycling way - Google Patents
Method for removing hydrogen sulfide from industrial gas in recycling way Download PDFInfo
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- CN101979130A CN101979130A CN2010105176740A CN201010517674A CN101979130A CN 101979130 A CN101979130 A CN 101979130A CN 2010105176740 A CN2010105176740 A CN 2010105176740A CN 201010517674 A CN201010517674 A CN 201010517674A CN 101979130 A CN101979130 A CN 101979130A
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- hydrogen sulfide
- manganese sulfate
- industrial gasses
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Abstract
The invention discloses a method for removing hydrogen sulfide from an industrial gas in a recycling way. The method mainly comprises the following steps of: feeding the hydrogen sulfide-containing industrial gas and air into a burning furnace to burn at the temperature of between 600 and 1,200 DEG C so as to obtain sulfur dioxide-containing high-temperature furnace gas; cooling the sulfur dioxide-containing high-temperature furnace gas to not more than 80 DEG C and humidifying; feeding the humidified and cooled sulfur dioxide-containing furnace gas into a pyrolusite pulp absorption system to directly contact the furnace gas with the pyrolusite pulp for absorption reaction so as to generate manganese sulfate-containing absorption tail solution; performing full absorption reaction and solid-liquid separation, wherein the obtained liquid phase is manganese sulfate-containing aqueous solution; and adding an impurity removing agent to react and then performing solid-liquid separation, wherein the obtained liquid phase is solution of manganese sulfate which is further processed. By implementing the method, the hydrogen sulfide can be removed and recovered from the industrial gas in a recycling way, the pollution of the hydrogen sulfide to atmosphere is reduced and controlled, the comprehensive utilization added value of the pyrolusite is improved, and meanwhile, the method has the characteristics of high sulfur-removing effect, high manganese utilization rate and light secondary pollution.
Description
Technical field
The present invention relates to a kind of is the hydrogen sulfide (H in the industrial gasses that removes of absorbent based on pyrolusite
2S) method is used for recycling industrial gas hydrogen sulfide (H
2S), be a kind of sulphur resource and method that fully utilizes the manganese resource recycled with the pyrolusite development and use.
Background technology
Sulfide hydrogen (the H that industries such as petrochemical industry, synthetic ammonia, coking chemical produce
2S) industrial gasses are a kind of pernicious gases, hydrogen sulfide (H
2S) existence not only can cause equipment and corrosion of piping, catalyst poisoning, and more seriously is to threaten personal safety, belongs to one of the environmental contaminants that must eliminate or control.About hydrogen sulfide (H in the above-mentioned industrial gasses
2Removing S) once developed many processing methods both at home and abroad, and these methods can be divided into wet method and dry method two big classes, and wherein wet method comprises absorption process and wet oxidation process again; Dry method then comprises iron oxide process, activated carbon method, sieve method, ion-exchange, electron beam irradiation method, membrane separation process, biochemical process desulfurization or the like.On the other hand, China is the country of a sulphur shortage of resources, therefore, and hydrogen sulfide (H in China's industrial gasses
2S) development trend of Chu Liing should be: reclaim the sulphur resource and combine with high-efficiency flue gas desulfurization, not only guarantee environmental benefit but also produce economic benefit.Ripe at present method of resource mainly is with the H in the industrial waste gas
2S makes raw material and produces sulfuric acid.
With the H in the industrial waste gas
2S makes raw material production sulfuric acid generally two lines: 1) earlier with H
2S makes sulphur, produces sulfuric acid with common sulphur-burning sulphuric acid plant then.This technology is the very general technology of domestic and international application, and China technology also be mature on the whole, except that the part key equipment, all can realize the production domesticization.H
2S produces the sulphur typical method Claus method and selective oxidation method.2) dispense Cross unit, with H
2S is that raw material is directly produced sulfuric acid.This method is flow process greatly simply, reduces investment outlay.H
2The direct process for preparing sulfuric acid of S divides 2 kinds of dry contact method and wet contact methods again.So-called dry contact method is exactly with H
2The S gas combustion becomes SO
2After, adopt the method with traditional pyrite-based sulfuric acid production resemble process again, comprise processing steps such as washing, drying, catalyzed conversion, absorption.So-called wet contact rule need not washing, drying, in the presence of steam sulfur dioxide is catalytically converted into sulfur trioxide exactly and also directly condenses into acid.As seen, wet contact method technology is more simple, helps the recovery of system thermal.When making raw material production sulfuric acid,, do not need to purify again, so adopt wet contact method suitable especially because hydrogen sulfide had carried out washing in separation process with the waste gas in the industry.Most representative technology is the wet method sulfur process (WSA technology) of rope company of Denmark Top, the cryogenic condensation technology and the Kang Kaite technology of German LURGI.From technological process, operating flexibility, energy consumption, recovery heat energy, to the mass fraction of sulfur recovery rate and product sulfuric acid, WSA technology all is better than other technologies.
Removing the existing multinomial Chinese patent of having applied for of method of hydrogen sulfide in the industrial gasses, is 200310106680.7 as application number, and name is called " method that removes hydrogen sulfide "; Application number is 02829106.9, and name is called " desulfurization and be used for the adsorbent of desulfurization "; Application number is 01818434.0, and name is called " method and apparatus that reclaims sulphur from gas stream containing hydrogen sulphide "; Application number is 200510017916.9, and name is called " a kind of method and apparatus of administering hydrogen sulfide tail gas ", and application number is 85109460, and name is called " hydrogen sulfide in the oxidation removal gas "; Application number is 96117610.5, and name is called " a kind of method that removes hydrogen sulfide from mist "; Application number: 03810326.5, name is called " method of selexol process ", and application number is: 200510095472.0, name is called " membrane adsorption natural gas desulfur method "; Application number is: 200610020946.X, and name is called " a kind of desulfurization dewatering purifying equipment for natural gas "; Application number is: 200710021732.9, and name is called " montmorillonite as natural gas desulfurizing agent "; Application number is: 200710023814.7, and name is called " montmorillonite natural-gas desulfurizer "; Application number is: " 200710023815.1 ", and name is called " method of selexol process "; Application number is: 02100334.3, and name is called " a kind of desulfurization formulation for natural gas "; Application number is: 200720039683.7, and name is called " montmorillonite as natural gas devulcanizer ".
All not relating in above-mentioned these patent application documents about the method that removes hydrogen sulfide from admixture of gas or equipment adopts pyrolusite pulp as absorbent.
Manganese sulfate is a kind of important chemical products, except can be used as chemical industry, metallurgical raw material, also can be used for the production of medicine, papermaking, pottery, catalyst, ore floatation, feed addictive, electrolytic manganese and the production of other manganese salt etc.Traditional manganese sulfate production method is relatively complicated, production method mainly contains two kinds: (1) manganese spar method: generally need with manganese content greater than 20% manganese spar powder, under 80～90 ℃ of conditions with the dilute sulfuric acid effect, generate manganese sulfate solution, then through purification and impurity removal, leave standstill, evaporative crystallization, centrifugation, make manganese sulfate through heated-air drying again.(2) pyrolusite method: will contain MnO
2Mix with 100: 20 quality proportioning with the anthracite powder at the pyrolusite powder more than 65%, in reduction roaster, carry out reduction roasting to produce MnO in 700 ℃-850 ℃, then MnO is cooled to room temperature under the condition of secluding air, cooled MnO dissolves with about 15% dilute sulfuric acid, make the manganese sulfate mother liquor through purification and impurity removal then, again through purification and impurity removal, leave standstill, evaporative crystallization, centrifugation, make manganese sulfate through heated-air drying again.These two kinds of manganese sulfate production methods all will consume a large amount of heats and sulfuric acid.
Adopt pyrolusite pulp to carry out the existing multinomial Chinese patent of having applied for of achievement in research of flue gas desulfurization, these patents are respectively: the patent No. is " absorbing the new method of sulphur dioxide production industrial manganic sulfate with pyrolusite pulp " of 89107720.0, the patent No. is 89104140.0, name is called " sulfur method of sulfur-containing smoke gas or tail gas ", the patent No. is 200420033268.7, name is called " flue gas desulfurization resource equipment ", the patent No. is 03135926.4.0, name is called " starching the method that absorbs SO 2 from fume and produce manganese sulfate with pyrolusite pulp and manganese spar ", the patent No. is 03135926.4.0, name is called " starching the method that absorbs SO 2 from fume and produce manganese sulfate with pyrolusite pulp and manganese spar ", and the patent No. is: 200510021926.X, name is called " is the method that composite absorber carries out exhuast gas desulfurization with pyrolusite and pH buffer ".
Above-mentioned these patented technologies with pyrolusite pulp absorbing and removing sulfur dioxide in flue gas, the method for clearly putting down in writing in the patent application document is to absorb sulfur dioxide in flue gas with pyrolusite pulp, does not all relate to this method is used for removing industrial gasses hydrogen sulfide (H
2S).
In sum, with the hydrogen sulfide (H in the industrial gasses
2S) making raw material produces the whole bag of tricks of sulfuric acid and includes two steps necessarys: the one, and the hydrogen sulfide (H in the industrial gasses
2S) burning generates SO
2, the 2nd, the SO of burning generation
2Be oxidized to SO
3, make sulfuric acid again.And adopt pyrolusite is that raw material is produced and needed to consume a large amount of heats and sulfuric acid in the conventional method of manganese sulfate, and this angle from the utilization of resources is a kind of waste.
Summary of the invention
At the hydrogen sulfide (H in the industrial gasses of prior art
2S) existing defective in the removal methods, purpose of the present invention are intended to propose a kind of new hydrogen sulfide (H
2S) remove and combine, and the desulfuration efficiency height with pyrolusite comprehensive utilization, manganese utilization rate height, secondary pollution is few, the method for remarkable in economical benefits, with reduce and control industrial gasses in hydrogen sulfide (H
2S) to the pollution of atmosphere, promote the hydrogen sulfide (H in the industrial gasses
2S) development of resource desulfur technology improves pyrolusite comprehensive utilization added value.
Purpose of the present invention realizes by the technical scheme that is made of following measure:
(1) sulfide hydrogen industrial gasses and air are sent into combustion furnace in 600 ℃～1200 ℃ burnings, obtain containing the high-temperature furnace gas of sulfur dioxide;
(2) high-temperature furnace gas that will contain sulfur dioxide is cooled to and is not higher than 80 ℃ and humidification;
(3) furnace gas that contains sulfur dioxide and pyrolusite pulp behind the decreasing temperature and increasing humidity are sent into desulfurization reactor, it is directly contacted carry out absorption reaction, generate the absorption tail washings of sulfur acid manganese, fully behind the absorption reaction, the furnace gas qualified discharge absorbs tail washings and enters next process;
(4) carry out Separation of Solid and Liquid to absorbing tail washings, add cleaner and carry out the removal of impurities reaction in the gained liquid phase, carry out Separation of Solid and Liquid after the removal of impurities reaction finishes, the gained liquid phase is the manganese sulfate liquid that can further process processing that will produce.
In such scheme, after the high-temperature furnace gas that contains sulfur dioxide preferably cools the temperature to 100 ℃～300 ℃ by heat transmission equipment earlier, again by humidifying cooling equipment humidification and cool the temperature to and be not higher than 80 ℃.The high-temperature furnace gas that will contain sulfur dioxide is cooled to 100 ℃～300 ℃ heat transmission equipment and preferably adopts waste heat boiler, the heat energy that produces with abundant recycling sulfide hydrogen industrial gasses burning.
The manganese sulfate solution that such scheme is produced can be produced all kinds of manganese products by further deep processing, as producing manganese sulfate through the purification and impurity removal evaporative crystallization, produces electrolytic manganese or manganese dioxide etc. through the purification and impurity removal electrolysis.As producing manganese sulfate with manganese sulfate solution, can take earlier it to be heated, make its evaporative crystallization reaction, crystallization reaction carries out Separation of Solid and Liquid after finishing, and the gained solid phase is the manganese sulfate finished product that will produce after drying.Liquid phase can be used for preparing pyrolusite pulp.The used steam of evaporative crystallization in the manganese sulfate finished product production process can be provided by the steam that waste heat boiler produces, and not need extra supply.
In such scheme, the solid-liquid mass ratio of described pyrolusite pulp is generally 1: (1～5), can be by powder pyrolusite, water or/and solid slag cleaning solution be mixed with.For the grade of the soft manganese of powder of preparing ore pulp, promptly its contained manganese dioxide ratio has no special requirements, but requires to be crushed to be not more than 100 orders.
In such scheme, described cleaner is at least a in oxidant, alkali lye and the vulcanizing agent, and described oxidant is selected from manganese oxide (MnO), hydrogen peroxide (H
2O
2) etc.; Described alkali lye is selected from limewash, ammoniacal liquor etc.; Described vulcanizing agent is selected from barium sulphide, sulfuration ammonia, DDTC etc.Impurity removal in the manganese sulfate solution is to generate sediment by the impurity reaction that adds in cleaner and the solution, and then removes impurity by Separation of Solid and Liquid.Therefore, the amount of the kind of cleaner adding and adding depends on the kind and the quantity of impurities in the pyrolusite pulp.
What disclose in the present invention is that absorbent removes in the method for hydrogen sulfide in the industrial gasses with the pyrolusite pulp, and the consumption of pyrolusite pulp can be recently definite according to the sulfide hydrogen industrial gasses amount manganese dioxide stoichiometry required with it.
The present invention discloses is that absorbent removes that the method for hydrogen sulfide has following very outstanding advantageous effect in the industrial gasses with the pyrolusite pulp:
(1) adopts the inventive method, traditional acid-making process that utilizes hydrogen sulfide in the industrial gasses and traditional production method of utilizing pyrolusite to generate manganese sulfate are combined, can with hydrogen sulfide in the industrial gasses remove with pyrolusite development and use combine, realize the complementation utilization of waste gas and lean ore, be a kind of green, the innovative technology of combined-circulation Economic concept.
(2) adopt the inventive method, the sulphur-containing exhaust gas that produces with the burning of hydrogen sulfide in the industrial gasses reacts with pyrolusite produces manganese sulfate, the waste heat that utilizes burning to produce is simultaneously produced steam and is used for the evaporative crystallization of manganese sulfate mother liquor, thereby sets up the recycling economy pattern that the hydrogen sulfide desulfurization combines with the development and use of pyrolusite in the cover industrial gasses.
(3) raw material pyrolusite used in the present invention is a natural crystal, and reserves are abundant, and low price, grade requirement not high (containing manganese 20～25% gets final product) only need Mechanical Crushing to 100 order to get final product during use.
(4) the present invention can realize resource, the innoxious and minimizing to hydrogen sulfide in the industry industrial gasses such as petrochemical industry, synthetic ammonia, coking chemical.The present invention not only can be used for the desulfurization of industry industrial gasses, also can be used for selexol process simultaneously.
(5) the present invention can realize the incrementization of pyrolusite comprehensive utilization be can be used for the comprehensive utilization of pyrolusite.
(6) method desulfuration efficiency height of the present invention, manganese utilization rate height, secondary pollution is few, remarkable in economical benefits.
Description of drawings
Fig. 1 is the technological process block diagram of one embodiment of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with process chart and by embodiment, but content of the present invention is not limited only to content related among the embodiment.
Embodiment 1:
The waste gas that present embodiment is administered is coking chemical sulfide hydrogen waste gas, and pending exhausted air quantity is 6000Nm
3/ h, mainly the consisting of of waste gas: H
2S 30%, CO
265%, N
24%.The technological process of present embodiment as shown in Figure 2.Earlier pyrolusite powder and water are mixed with liquid-solid ratio (mass ratio) and are 3: 1 ore pulp in the pulp tank of agitator is housed, ore pulp is squeezed in the desulfurization reactor by inlet by the ore pulp pump.Start the main blower that is arranged on the combustion furnace rear end, make combustion furnace be in negative pressure state, contain H
2The waste gas of S and air are drawn into burning together in the combustion furnace by pipeline by negative pressure, and ignition temperature is controlled at about 1000 ℃.The SO that contains that burns and generate
2High-temperature furnace gas, it is standby for follow-up manganese sulfate evaporative crystallization drying process to enter into waste heat boiler production steam, is cooled to about 300 ℃, contains SO then
2Furnace gas enters into the further humidification of humidifying cooling tower again and cools to about 70 ℃.Contain SO behind the humidifying cooling
2Furnace gas enters in the desulfurization reactor, enters in the ore pulp and is absorbed by gas dispersion apparatus is set in the reactor.SO in the flue gas
2Carry out absorption reaction with the pyrolusite absorbent, with the SO in the waste gas
2Absorbing and removing, the gas after the absorption processing is up to standard is by the gas vent discharging of desulfurization reactor.The absorption tail washings that contains manganese sulfate, slag and water is discharged from the ore pulp outlet of desulfurization reactor and is sent to the sedimentation separation pond, after abundant sedimentation, the supernatant that contains suspension is driven into filter separator by slush pump, and water miscible manganese sulfate is separated with solid slag, and liquid phase is a manganese sulfate solution.Manganese sulfate solution is sent to the impurity and purification pond carries out purified treatment.In the impurity and purification unit, at first add MnO to manganese sulfate solution
2Oxidant is with contained Fe
2+Oxidation of impurities is Fe
3+, in manganese sulfate solution, add limewash (or ammoniacal liquor) again, manganese sulfate solution pH value is adjusted to about 6.0, make the Fe in the manganese sulfate solution
3+, Al
3+Precipitated removal; In manganese sulfate solution, add barium sulphide (or vulcanizing ammonia, DDTC) again and make heavy metal ion Cu
2+, Pb
2+, Co
2+, Ni
2+Precipitated removal; Then manganese sulfate solution is heated to the adularescent flocky precipitate and occurs, make silicic acid, Mg in the manganese sulfate solution
2+Be removed; Afterwards manganese sulfate solution was left standstill about 24 hours, remove Ca in the manganese sulfate solution with precipitation
2+Obtain purer manganese sulfate solution through after the above-mentioned processing, obtain manganese sulfate through the reaction of heating evaporation condensing crystallizing again, can obtain product manganese sulfate in about two hours to manganese sulfate in drying under 150 ℃～200 ℃ the condition at last.
Embodiment 2:
The waste gas that present embodiment is administered is coking chemical sulfide hydrogen waste gas, and pending exhausted air quantity is 6000Nm
3/ h, mainly the consisting of of waste gas: H
2S 30%, CO
265%, N
24%.The technological process of present embodiment as shown in Figure 1.With pyrolusite powder with to be mixed with liquid-solid ratio (mass ratio) with water in the pulp tank of agitator is housed be 5: 1 ore pulp, ore pulp is squeezed in the desulfurization reactor by inlet earlier by the ore pulp pump.Start the main blower that is arranged on the combustion furnace rear end, make combustion furnace be in negative pressure state, contain H
2The waste gas of S and air are drawn into burning together in the combustion furnace by pipeline by negative pressure, and ignition temperature is controlled at about 700 ℃.The SO that contains that burns and generate
2High-temperature furnace gas enters heat exchanger, contains SO after being cooled to about 200 ℃
2Furnace gas enters into the humidifying cooling tower again to carry out humidification and cools to about 60 ℃.Contain SO behind the humidifying cooling
2Furnace gas enters in the desulfurization reactor, is entered in the ore pulp by gas dispersion apparatus to be absorbed again.SO in the flue gas
2Carry out absorption reaction with the pyrolusite absorbent, with the SO in the waste gas
2Absorbing and removing absorbs gas after up to standard by the gas vent discharging of desulfurization reactor.The absorption tail washings that contains manganese sulfate, slag and water is discharged from the ore pulp outlet of desulfurization reactor and is sent to the sedimentation separation pond, after abundant sedimentation, the supernatant that contains suspension is driven into filter separator by slush pump, and water miscible manganese sulfate is separated with solid slag, and liquid phase is a manganese sulfate solution.Manganese sulfate solution is sent to the impurity and purification pond carries out purified treatment.In the impurity and purification unit, at first add MnO to manganese sulfate solution
2Oxidant is with contained Fe
2+Oxidation of impurities is Fe
3+, in manganese sulfate solution, add limewash (or ammoniacal liquor) again, manganese sulfate solution pH value is adjusted to about 5.0, make the Fe in the manganese sulfate solution
3+, Al
3+Precipitated removal; In manganese sulfate solution, add barium sulphide (or vulcanizing ammonia, DDTC) again and make heavy metal ion Cu
2+, Pb
2+, Co
2+, Ni
2+Precipitated removal; Then manganese sulfate solution is heated to the adularescent flocky precipitate and occurs, make silicic acid, Mg in the manganese sulfate solution
2+Be removed; Then manganese sulfate solution was left standstill about 24 hours, remove Ca in the manganese sulfate solution with precipitation
2+Obtain purer manganese sulfate solution through after the above-mentioned processing.
Claims (10)
1. a resource removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that mainly comprising following processing step:
(1) sulfide hydrogen industrial gasses and air are sent into combustion furnace in 600 ℃～1200 ℃ burnings, obtain containing the high-temperature furnace gas of sulfur dioxide;
(2) high-temperature furnace gas that will contain sulfur dioxide is cooled to and is not higher than 80 ℃ and humidification;
(3) furnace gas that contains sulfur dioxide and pyrolusite pulp behind the decreasing temperature and increasing humidity are sent into desulfurization reactor, it is directly contacted carry out absorption reaction, generate the absorption tail washings of sulfur acid manganese, fully behind the absorption reaction, the furnace gas qualified discharge absorbs tail washings and enters next process;
(4) carry out Separation of Solid and Liquid to absorbing tail washings, add cleaner and carry out the removal of impurities reaction in the gained liquid phase, carry out Separation of Solid and Liquid after the removal of impurities reaction finishes, the gained liquid phase is the manganese sulfate liquid that can further process processing that will produce.
2. resource according to claim 1 removes the method for hydrogen sulfide in the industrial gasses, after the high-temperature furnace gas that it is characterized in that containing sulfur dioxide cools the temperature to 100 ℃～300 ℃ by heat transmission equipment earlier, cool the temperature to by humidifying cooling equipment again and be not higher than 80 ℃.
3. resource according to claim 2 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that it is waste heat boiler that the high-temperature furnace gas that will contain sulfur dioxide is cooled to 100 ℃～300 ℃ heat transmission equipment.
4. remove the method for hydrogen sulfide in the industrial gasses according to claim 1 or 2 or 3 described resources, it is characterized in that the manganese sulfate solution of gained is heated, make its evaporative crystallization reaction, crystallization reaction carries out Separation of Solid and Liquid after finishing, and the gained solid phase is the manganese sulfate finished product that will produce after drying.
5. resource according to claim 4 removes the method for hydrogen sulfide in the industrial gasses, and the solid-liquid mass ratio that it is characterized in that described pyrolusite pulp is 1: (1～5), by powder pyrolusite, water or/and solid slag cleaning solution be mixed with.
6. resource according to claim 5 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that the powder of described powder pyrolusite is not more than 100 orders.
7. resource according to claim 4 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that described cleaner is at least a in oxidant, alkali lye and the vulcanizing agent.
8. resource according to claim 7 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that described oxidant is selected from manganese oxide and hydrogen peroxide.
9. resource according to claim 7 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that described alkali lye is selected from limewash and ammoniacal liquor.
10. resource according to claim 7 removes the method for hydrogen sulfide in the industrial gasses, it is characterized in that described vulcanizing agent is selected from barium sulphide, sulfuration ammonia and DDTC.
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|---|---|---|---|---|
| CN102380305A (en) * | 2011-09-30 | 2012-03-21 | 合肥宁垣工程技术有限责任公司 | Technology and apparatus for desulphurizing acidic gas |
| CN102390868A (en) * | 2011-08-22 | 2012-03-28 | 青海华信冶炼有限公司 | Method for producing manganese sulfate from smelting furnace gas |
| CN102815750A (en) * | 2012-09-04 | 2012-12-12 | 湖南汇通科技有限责任公司 | Method for preparing manganese sulfate by using manganese dioxide ore pulp to absorb sulfur dioxide in flue gases |
| CN106039964A (en) * | 2016-07-06 | 2016-10-26 | 扬州大学 | Method for desulfurization cogenerating of hydrogen and sulfuric acid |
| CN109987636A (en) * | 2019-05-05 | 2019-07-09 | 刘向东 | A kind of energy-saving new technology of manganese sulphate |
| CN115159470A (en) * | 2022-08-02 | 2022-10-11 | 广西埃索凯新材料科技有限公司 | Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur |
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| CN1772345A (en) * | 2005-10-25 | 2006-05-17 | 四川大学 | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent |
| CN101574617A (en) * | 2009-06-12 | 2009-11-11 | 四川大学 | Synchronous desulphrization and denitration method of flue gas pyrolusite pulp for reclamation |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390868A (en) * | 2011-08-22 | 2012-03-28 | 青海华信冶炼有限公司 | Method for producing manganese sulfate from smelting furnace gas |
| CN102390868B (en) * | 2011-08-22 | 2013-06-26 | 青海华信冶炼有限公司 | Method for producing manganese sulfate from smelting furnace gas |
| CN102380305A (en) * | 2011-09-30 | 2012-03-21 | 合肥宁垣工程技术有限责任公司 | Technology and apparatus for desulphurizing acidic gas |
| CN102815750A (en) * | 2012-09-04 | 2012-12-12 | 湖南汇通科技有限责任公司 | Method for preparing manganese sulfate by using manganese dioxide ore pulp to absorb sulfur dioxide in flue gases |
| CN102815750B (en) * | 2012-09-04 | 2014-09-17 | 湖南汇通科技有限责任公司 | Method for preparing manganese sulfate by using manganese dioxide ore pulp to absorb sulfur dioxide in flue gases |
| CN106039964A (en) * | 2016-07-06 | 2016-10-26 | 扬州大学 | Method for desulfurization cogenerating of hydrogen and sulfuric acid |
| CN106039964B (en) * | 2016-07-06 | 2018-12-11 | 扬州大学 | A kind of method of desulfurization co-producing hydrogen and sulfuric acid |
| CN109987636A (en) * | 2019-05-05 | 2019-07-09 | 刘向东 | A kind of energy-saving new technology of manganese sulphate |
| CN115159470A (en) * | 2022-08-02 | 2022-10-11 | 广西埃索凯新材料科技有限公司 | Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur |
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