CN102935327A - Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln - Google Patents

Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln Download PDF

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CN102935327A
CN102935327A CN2012104824020A CN201210482402A CN102935327A CN 102935327 A CN102935327 A CN 102935327A CN 2012104824020 A CN2012104824020 A CN 2012104824020A CN 201210482402 A CN201210482402 A CN 201210482402A CN 102935327 A CN102935327 A CN 102935327A
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tail gas
sulfuric acid
liquid
sulfur dioxide
chromium
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CN2012104824020A
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CN102935327B (en
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李先荣
陈宁
王方兵
黄先东
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四川省安县银河建化(集团)有限公司
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Abstract

The invention relates to a method for removing sulfur dioxide in tail gas from an industrial kiln, which comprises the following step: enabling a hexavalent-chromium-containing sodium hydrogen sulfate solution used as an oxidizing absorption solution to be in contact with the tail gas from the industrial kiln, thus removing sulfur dioxide in the tail gas from the industrial kiln, wherein the hexavalent-chromium-containing sodium hydrogen sulfate solution is a byproduct in the chrome acid anhydride production process based on a sulfuric acid method. The invention also relates to a method for comprehensively utilizing the hexavalent-chromium-containing sodium hydrogen sulfate solution byproduct in the chrome acid anhydride production process based on a sulfuric acid method and the tail gas from the industrial kiln, which comprises the following step: enabling the hexavalent-chromium-containing sodium hydrogen sulfate solution used as an oxidizing absorption solution to be in contact with the tail gas from the industrial kiln, thus removing sulfur dioxide in the tail gas from the industrial kiln, and obtaining carbon dioxide gas and an oxidizing absorption finished solution containing chromium sulfate, sodium hydrogen sulfate and sulfuric acid, wherein the hexavalent-chromium-containing sodium hydrogen sulfate solution is a byproduct in the chrome acid anhydride production process based on a sulfuric acid method. According to the method for removing sulfur dioxide, the operating cost is low, and the sulfur dioxide removal rate is high. According to the comprehensive utilization method, the comprehensive utilization rate is high.

Description

Remove the method for the sulfur dioxide in the Industrial Stoves tail gas and the method for comprehensive utilization Industrial Stoves tail gas
Technical field
The present invention relates to a kind of method with the sulfur dioxide removal in the Industrial Stoves tail gas, and the method that chromyl sodium bisulfate and Industrial Stoves tail gas at Production By Sulfuric Acid Process chromic anhybride byproduct in process are fully utilized.
Background technology
Start late aspect the improvement of China's sulfur dioxide in industrial tail gas, technological means is still immature so far.The flue gas desulfur device of more domestic power plant be from Europe, the technology introduced of the U.S., Japan; Some technology or experimental, not full maturity; Simultaneously, the flue gas treating capacity of equipment is very little, can not satisfy industry and environmental requirement.Along with country more and more payes attention to environmental protection, desulfurization project has become the essential input project of all new power plant construction.In recent years, China is take external technology as the basis, researched and developed gradually the desulfur technology that is fit to oneself needs.Common desulfurizing method of exhaust gas has limestone-gypsum method, two alkaline process, simple and easy ammonia process, ammonia process, magnesium oxide method, sulfonated phthalocyanine cobalt doctor treatment, spray drying process, in-furnace calcium spraying and afterbody humidification etc.It below is certain methods comparatively ripe in the desulfur technology of domestic use.
Desulfurization method of limestone-gypsum technique is most widely used a kind of desulfur technology in the world, and about 90% in the used flue gas desulfur device in thermal power plant of Japan, Germany, the U.S. all adopts this technique.Its operation principle is as follows: agstone is added water make slurries, pump in the absorption tower as absorbent, and fully contact mixing with flue gas, sulfur dioxide in the flue gas and the calcium carbonate in the slurries and the air that blasts from the tower bottom carry out oxidation reaction and generate calcium sulfate, after calcium sulfate reached certain saturation degree, crystallization formed two hydrated gypsum.The gypsum slurries that to discharge from the absorption tower is concentrated, and dehydration makes its water content less than 10 % by weight, then delivers to the gypsum bunker and stacks.Utilize the droplet in the flue gas after demister is removed desulfurization, behind the heat exchanger heat temperature raising, enter atmosphere by chimney.Owing to by circulating pump the absorbent slurry in the absorption tower being circulated and it being contacted with flue gas, the absorbent utilization rate is very high, and calcium sulfur ratio is lower, and desulfuration efficiency can be greater than 95%.
Spray drying process is take lime as desulfurization absorbent, its basic principle is as follows: with the quick lime slaking and add water and make the calcium hydroxide breast, the calcium hydroxide breast is pumped into the atomising device that is arranged in the absorption tower, be atomized into the absorbent of fine drop and mix with flue gas in the absorption tower and contact, and with flue gas in SO 2Chemical reaction occurs generate CaSO 3, and then with the SO in the flue gas 2Remove.Meanwhile, absorbent becomes dry because the moisture of bringing into evaporates rapidly, and flue-gas temperature decreases.Desulfurization reaction product and unemployed absorbent are taken out of the absorption tower with the form of dried particles thing by flue gas, enter deduster and are collected.Flue gas after the desulfurization discharges after the deduster dedusting.The spray drying process sulfur removal technology possesses skills, and maturation, technological process are comparatively simple, the system reliability high, and desulfurization degree can reach more than 85%.Desulfurization ash can be used for brickmaking, builds the road, but is to abandon to ash field or the waste and old pit of backfill more.
Ammonia scrubbing method sulfur removal technology is take ammoniacal liquor as absorbent, and by-product can be used as the ammonium sulfate of chemical fertilizer.The flue gas that utilizes flue gas heat-exchange unit that boiler is discharged is cooled to 90-100 ℃, enters the washing of pre-wash device and removes HCl and HF, and the flue gas after the washing enters in the preposition washer after removing water droplet through liquid drop separator.In preposition washer, from cat head spray ammonia scrubbing flue gas, the SO in the flue gas 2Be washed to absorb and remove, the flue gas of washing is discharged, utilize liquid drop separator to remove the water droplet that it carries, enter desulfurizing scrubber.In this washer, utilize ammoniacal liquor further to wash flue gas, utilize the demister at scrubbing tower top to remove droplet, after flue gas heat-exchange unit heating by smoke stack emission.Be that about 30% ammonium sulfate is discharged from scrubbing tower with the concentration that produces in the washing process, deliver to chemical fertilizer factory and further process or directly sell as liquid nitrogen fertilizer, also the further evaporating, concentrating and drying of described solution can be processed into particle, crystal or block chemical fertilizer and sell.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly at correlative technology field, in the hope of obtaining a kind of method with the sulfur dioxide removal in the Industrial Stoves tail gas.Found that and to contact and the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed with Industrial Stoves tail gas as the oxidation absorption liquid by making the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process.The inventor just is being based on above-mentioned discovery and is finishing the present invention, and has developed on this basis a kind of comprehensive utilization in the method for chromyl sodium bisulfate and the Industrial Stoves tail gas of Production By Sulfuric Acid Process chromic anhybride byproduct in process.
Therefore, the purpose of this invention is to provide a kind of method with the sulfur dioxide removal in the Industrial Stoves tail gas.
Another purpose of the present invention provides a kind of comprehensive utilization in the method for chromyl sodium bisulfate and the Industrial Stoves tail gas of Production By Sulfuric Acid Process chromic anhybride byproduct in process.
The technical scheme that realizes the object of the invention can be summarized as follows:
1. method with the sulfur dioxide removal in the Industrial Stoves tail gas, described method comprises: the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed.
2. according to the 1st method, wherein said chromyl sodium bisulfate comprises with Na 2Cr 2O 72H 2O counts the Cr VI of 5-60 % by weight and the niter cake of 1-15 % by weight, and its acid number is with H 2SO 4Count 50-800g/l.
3. according to the 1st method, wherein be dissolved in the water by the melting niter cake that will in Production By Sulfuric Acid Process chromic anhybride process, generate and Separation of Solid and Liquid obtains chromyl sodium bisulfate as the oxidation absorption liquid.
4. a comprehensive utilization is in the method for chromyl sodium bisulfate and the Industrial Stoves tail gas of Production By Sulfuric Acid Process chromic anhybride byproduct in process, and described method comprises:
Chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed, and the acquisition carbon dioxide is finished liquid with the oxidation absorption that comprises chromium sulfate, niter cake and sulfuric acid; With
Carbon dioxide is used for roasting chromite prepares sodium chromate, therein the sodium chromate alkaline solution is neutralized; Perhaps carbon dioxide is used for carbonizatin method and produces sodium dichromate, with therein with chromium acid sodium solution carbonization or pre-carbonization.
5. according to the 4th method, wherein said chromyl sodium bisulfate comprises with Na 2Cr 2O 72H 2O counts the Cr VI of 5-60 % by weight and the niter cake of 1-15 % by weight, and its acid number is with H 2SO 4Count 50-800g/l.
6. according to the 4th method, wherein be dissolved in the water by the melting niter cake that will in Production By Sulfuric Acid Process chromic anhybride process, generate and Separation of Solid and Liquid obtains chromyl sodium bisulfate as the oxidation absorption liquid.
7. according to each method among the 4-6, described method comprises also that separation of oxygenated absorbs to be finished liquid and obtains tanning with chromium powder and dilute sulfuric acid, and described dilute sulfuric acid is used for the reduction of chromate waste water as acidulant.
8. according to each method among the 4-6, described method also comprises utilizes three (C 8-10Alkyl) amine absorbs oxidation and finishes liquid and carry out extract and separate, obtain thus the vitriolated extract of bag and comprise chromium sulfate and the raffinate of niter cake, and the raffinate that will describedly comprise chromium sulfate and niter cake is as the raw material of making tanning and use chromium powder.
9. according to the 8th method, wherein utilize three iso-octyl amine that liquid is finished in the oxidation absorption and carry out extract and separate.
10. according to the 8th or 9 method, described method comprises that also the vitriolated extract of water reextraction bag obtains dilute sulfuric acid, and it is used for the reduction of chromate waste water as acidulant.
The method operating cost that removes sulfur dioxide of the present invention is low; The sulfur dioxide removal rate is high; And optionally wherein sulfur dioxide is removed.
Method of comprehensive utilization of the present invention can effectively utilize at the chromyl sodium bisulfate of Production By Sulfuric Acid Process chromic anhybride byproduct in process and Industrial Stoves tail gas, and obtains useful carbon dioxide, chromium powder and dilute sulfuric acid, and comprehensive utilization ratio is high.
These and other purposes, features and advantages of the present invention will be easy to be understood by those of ordinary skill after integral body is considered the present invention.
The specific embodiment
The term that uses in the context of the invention " Cr VI " refers to the chromium element that exists with+6 valencys, i.e. Cr 6+In alkaline solution, it is with CrO 4 2-Form exist; In acid solution, it is with Cr 2O 7 2-Form exist.
The present application people produces actual in conjunction with chromium salt factory, according to the redox principle, and the method that has proposed first to utilize the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process that the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed.
One aspect of the present invention provides a kind of method with the sulfur dioxide removal in the Industrial Stoves tail gas, described method comprises: the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed.
The method that removes sulfur dioxide of the present invention is particularly suitable for the sulfur dioxide removal that will be rich in the Industrial Stoves tail gas of carbon dioxide.
The present invention provides the method for a kind of comprehensive utilization at chromyl sodium bisulfate and the Industrial Stoves tail gas of Production By Sulfuric Acid Process chromic anhybride byproduct in process on the other hand, described method comprises: the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed, and the acquisition carbon dioxide is finished liquid with the oxidation absorption that comprises chromium sulfate, niter cake and sulfuric acid.
The Production By Sulfuric Acid Process chromic anhybride is well known to those skilled in the art, and its related main reaction is as follows: Na 2Cr 2O 7+ 2H 2SO 4=2CrO 3+ 2NaHSO 4+ H 2O.The Production By Sulfuric Acid Process chromic anhybride comprises the concentrated sulfuric acid and sodium dichromate mother liquor or sodium dichromate are carried out frit reaction under the temperature about 200 ℃; Standing demix after reaction is finished, wherein lower floor is the chromic anhybride of melting, the upper strata fused materials is the mixture of the complete sulfuric acid of niter cake, unreacted and the chromic anhybride do not separated of part; After layering reaches separation requirement, take out lower floor's chromic anhybride, film-making in pelleter, then cooling obtains chromic anhydride products.Take out the upper strata fused materials, and it is soluble in water, for example by filtration or decant water-insoluble is removed and obtained chromyl sodium bisulfate, and used as the oxidation absorption liquid.Water-insoluble is the Cr that a small amount of chromic anhybride at high temperature decomposes generation 3+Chromic sodium alum (Na with the sulfuric acid reaction generation 3Cr (SO 4) 3).Can with the deposition water-insoluble for the manufacture of chrome tanning agent.
Described chromyl sodium bisulfate comprises with Na 2Cr 2O 72H 2O counts the Cr VI of 5-60 % by weight and the niter cake of 1-15 % by weight, and its acid number is that 50-800g/l is (with H 2SO 4Meter).
The instantiation of Industrial Stoves tail gas includes but not limited to limekiln calcining tail gas, cement kiln tail gas and chromite calcining kiln tail gas.Different according to its source, the content of carbon dioxide can be 1-99 volume % in the Industrial Stoves tail gas, and content of sulfur dioxide is generally 0.1-10 volume %.For example, the CO of limekiln calcining tail gas 2Content is 30-45 volume %, and content of sulfur dioxide is 1-3 volume %; The CO of cement kiln tail gas 2Content is 12-20 volume %, and content of sulfur dioxide is 0.1-1 volume %; The CO of chromite calcining kiln tail gas 2Content is 10-15 volume %, and content of sulfur dioxide is 1-3 volume %.Before making chromyl sodium bisulfate and Industrial Stoves tail gas contact, if need and can carry out preliminary treatment to Industrial Stoves tail gas, for example cooling, dedusting.
Any suitable method that contacts known to can those skilled in the art of chromyl sodium bisulfate and Industrial Stoves tail gas carries out, and for example gas-liquid counter current contact, Industrial Stoves tail gas is passed in the chromyl sodium bisulfate.Preferably make chromyl sodium bisulfate and Industrial Stoves tail gas carry out counter current contacting, for example in absorption tower or aeration tower.
Being applicable to absorption tower of the present invention or aeration tower is well known to those skilled in the art.Via pump chromyl sodium bisulfate is injected from cat head, optional pretreated Industrial Stoves tail gas is passed at the bottom of tower, the chromyl sodium bisulfate that flows downward is fully contacted with the Industrial Stoves tail gas adverse current that upwards flows, the oxidation absorption is finished liquid and is discharged at the bottom of tower, and the carbon dioxide that removes the sulfur dioxide gained is discharged from cat head.If necessary, can be in tower bottom or bottom a part of oxidation be absorbed and finish liquid and be recycled to cat head.According to the concrete behaviour in service of chromyl sodium bisulfate, for example with Na 2Cr 2O 72H 2The content of 6-valence Cr ions of O meter, those skilled in the art can determine that the oxidation that recycles absorbs and finish liquid and the oxidation absorption of taking out finish the proper ratio of liquid between the two at the bottom of tower.For the sulfur dioxide in the Industrial Stoves tail gas is removed fully, those skilled in the art can be according to physical parameter such as tower height, tower volume or the theoretical cam curve etc. of tower, in the content of sulfur dioxide in the Industrial Stoves tail gas and the chromyl sodium bisulfate with Na 2Cr 2O 72H 2The content of 6-valence Cr ions of O meter is reasonably determined Industrial Stoves tail gas and chromyl sodium bisulfate flow separately.
Sulfur dioxide in the Industrial Stoves tail gas absorbed to be fixed on obtain oxidation in the chromyl sodium bisulfate and absorb and finish liquid and carbon dioxide.According to the inventive method, the removal efficiency of the sulfur dioxide in the Industrial Stoves tail gas can reach more than 95%.
Oxidation absorbs finishes chromium sulfate, 1-5 % by weight niter cake and the 1-5 % by weight sulfuric acid that liquid mainly comprises the generation of 10-20 % by weight hexavalent chrome reduction.
The carbon dioxide that meets emission request directly can be entered in the atmosphere.Yet, preferably use it in other industrial manufacture process, to reduce greenhouse gas emissions.
For this reason, method of comprehensive utilization of the present invention also comprises carbon dioxide is used for other industrial manufacture process, for example is used for roasting chromite and prepares sodium chromate, therein the sodium chromate alkaline solution is neutralized; Perhaps be used for carbonizatin method and produce sodium dichromate, with therein with chromium acid sodium solution carbonization or pre-carbonization.If necessary, before using it for other industrial manufacture process, can be further processed carbon dioxide, for example purifying.
The gained carbon dioxide can be used for roasting chromite and prepare sodium chromate, therein the sodium chromate alkaline solution is neutralized to pH as 8.5-9.5.It is known to those skilled in the art to obtain the sodium chromate alkaline solution by roasting chromite and leaching.The concentration of sodium chromate alkaline solution is generally 200-600gL -1(with Na 2CrO 44H 2The O meter), basicity is 10-100gL -1(with Na 2CO 3Meter).The consumption of carbon dioxide is as the criterion will be neutralized to by the sodium chromate alkaline solution that roasting chromite and leaching obtain required pH number range.Advantageously, before carrying out this step, the temperature of sodium chromate alkaline solution is controlled between 90-105 ℃.Separate with sodium chromate alkaline solution gained mixture in inciting somebody to action, to remove solid impurity wherein.Then, the pH value of utilizing acid chromium-containing solution to regulate gained solution is adjusted to 7.0-8.5.Acid chromium-containing solution is that carbonizatin method prepares pre-carbodiimide solution, carbodiimide solution, electrolyte, dehydration mother liquor, waste water or the wash water that produces in the sodium dichromate process, utilizes the solution of sodium dichromate preparation, or its any mixed solution.Prepare in the sodium dichromate process at carbonizatin method and to obtain pre-carbodiimide solution in the chromium acid sodium solution by carbon dioxide is passed into, its concentration is 300-500gL -1(with Na 2Cr 2O 72H 2The O meter), pH is 6.5-7.0.Prepare in the sodium dichromate process at carbonizatin method and to obtain carbodiimide solution in the chromium acid sodium solution by carbon dioxide is passed into, its concentration is 900-1000gL -1(with Na 2Cr 2O 72H 2The O meter), pH is 5.5-6.2.Prepare in the sodium dichromate process at carbonizatin method and by the mode of electrolysis carbodiimide solution to be replenished acidifying and obtain electrolyte, its concentration is 900-1000gL -1(with Na 2Cr 2O 72H 2The O meter), pH is 0.5-1.5.By the sodium dichromate crystal separation is obtained the mother liquor that dewaters, its concentration is 1000-1400gL after carbonizatin method prepares the sodium dichromate Crystallization -1(with Na 2Cr 2O 72H 2The O meter), pH is 0.5-1.5.Waste water is the feed liquid that carbonizatin method prepares quality dissatisfaction in the sodium dichromate process, and its concentration is 300-400gL -1(with Na 2Cr 2O 72H 2The O meter), pH is 0.5-7.0.Prepare in the sodium dichromate process at carbonizatin method and to obtain wash water by the sodium acid carbonate that washes by-product with water, its concentration is 100-400gL -1(with Na 2Cr 2O 72H 2The O meter), pH is 5.5-7.0.The consumption of acid chromium-containing solution is adjusted to required number range with the pH value with gained solution and is as the criterion.By evaporation gained solution is concentrated, so that its concentration is controlled at Na 2CrO 44H 2O counts 900-1100gL -1Thereby, be conducive to the sodium chromate crystallization.To concentrate gained solution and be cooled to 26-68 ℃, so that the sodium chromate crystallization.Then separate by conventional meanses such as centrifugal, suction filtration or press filtrations and obtain the sodium chromate product.
The more information of just being correlated with " carbon dioxide is used for roasting chromite prepares sodium chromate; therein the sodium chromate alkaline solution is neutralized ", but the application reference people is in the application for a patent for invention that is entitled as " a kind of method for preparing sodium chromate " of submitting on the same day.At this, by reference its integral body is attached to herein.
" carbon dioxide is used for carbonizatin method produces sodium dichromate, with therein with chromium acid sodium solution carbonization or pre-carbonization " is known to those skilled in the art.
Method of comprehensive utilization of the present invention comprises further that separation of oxygenated absorbs and finishes liquid and obtain the tanning chromium powder.Tanning is chromium sulfate basic and sodium sulphate with the main component of chromium powder.For example, can utilize three (C 8-10Alkyl) amine absorbs oxidation and finishes liquid and carry out extract and separate, obtain thus the vitriolated extract of bag and comprise chromium sulfate and the raffinate of niter cake, and the raffinate that will describedly comprise chromium sulfate and niter cake is as the raw material of making tanning and use chromium powder.Utilizing the described raffinate that comprises chromium sulfate and niter cake to make tanning uses chromium powder known to those skilled in the art.Three (C 8-10Alkyl) instantiation of amine is three iso-octyl amine.
Method of comprehensive utilization of the present invention comprises further that separation of oxygenated absorbs to be finished liquid and obtains dilute sulfuric acid, and it is used for the reduction of chromate waste water as acidulant.For example, the vitriolated extract acquisition of water reextraction bag acid number is 50-200gL -1(with H 2SO 4Meter) dilute sulfuric acid, and it is used for the reduction of chromate waste water as acidulant.
Remove in the method for Industrial Stoves sulfur dioxide in tail gas in the present invention, used oxidation absorption liquid is the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process, and is with low cost; The disposal ability of oxidation absorption liquid is strong, and the sulfur dioxide removal rate is high; And optionally the sulfur dioxide in the Industrial Stoves tail gas is removed, can not affect its carbon dioxide content, this is conducive to the recycling of carbon dioxide; Sulfur dioxide in the tail gas is absorbed and is fixed in the oxidation absorption liquid, has reclaimed rationally and effectively the sulphur resource.
In the method for the chromyl sodium bisulfate of Production By Sulfuric Acid Process chromic anhybride byproduct in process and Industrial Stoves tail gas, used oxidation absorption liquid is the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process in the present invention comprehensive utilization; The gained carbon dioxide can be used for other industrial manufacture process, for example roasting chromite prepares sodium chromate or carbonizatin method is produced sodium dichromate; Can absorb to finish from oxidation and separate acquisition tanning chromium powder and dilute sulfuric acid the liquid, wherein the latter can for example be used for the reduction of chromate waste water as acidulant; Described method synthesis utilization rate is high.
The inventive method technique is reasonable, energy consumption is low, can effectively recycle chromium sulphur resource, non-secondary pollution.
Embodiment
Hereinafter by reference example the present invention is specifically described, but described embodiment does not consist of any restriction to the scope of the invention.
Embodiment 1
The melting niter cake that will generate in Production By Sulfuric Acid Process chromic anhybride process is soluble in water, and the acquisition content of 6-valence Cr ions is 168gL -1(with Na 2Cr 2O 72H 2The O meter), niter cake content is that 11.2 % by weight and acid number are 515gL -1(with H 2SO 4Meter) chromyl sodium bisulfate, and used as the oxidation absorption liquid, with pump with this oxidation absorption liquid with 10m 3The flow of/h is of a size of from the cat head input In the absorption tower of 1000mm * 10000mm.To dewater from the calcining tails dedusting in limekiln, use air blast with 20000m 3The flow of/h passes into the absorption tower at the bottom of tower.In described limekiln calcining tail gas, the content of carbon dioxide is 32 volume %, and the content of sulfur dioxide is 2.3 volume %.Make oxidation absorption liquid and limekiln calcining tail gas at normal temperatures and pressures in the absorption tower counter current contacting form oxidation and absorb and finish liquid, simultaneously at the bottom of tower with pump with 50m 3The flow of/h is finished liquid with the oxidation absorption and is recycled to cat head.Liquid is finished in the oxidation absorption taken out at the bottom of tower, the carbon dioxide that has removed sulfur dioxide is then discharged from cat head.The oxidation absorption is finished liquid and is comprised 11.5 % by weight chromium sulfates, 1.3 % by weight niter cakes and 1.4 % by weight sulfuric acid.The content of carbon dioxide is 32.7 volume % in the described carbon dioxide.The removal efficiency of the sulfur dioxide in the limekiln calcining tail gas is 96%.
At the bottom of tower, take out 10m 3Oxidation absorbs finishes liquid, and uses 1.5m 3Trioctylphosphine amine extraction 3 times, chromic content is 68.5gL in the raffinate -1(with Cr 2O 3Meter).Described raffinate is delivered to the chromium powder manufacturing shop as making tanning with the feedstock pump of chromium powder.
Use 2m 3Water is with 2m 3Extract is stripped 3 times, obtains 2.5m 3Dilute sulfuric acid, its acid number are 85gL -1(with H 2SO 4Meter).This dilute sulfuric acid is used for the reduction of chromate waste water as acidulant.
Embodiment 2
The melting niter cake that will generate in Production By Sulfuric Acid Process chromic anhybride process is soluble in water, and the acquisition content of 6-valence Cr ions is 220gL -1(with Na 2Cr 2O 72H 2The O meter), niter cake content is that 5.7 % by weight and acid number are 573gL -1(with H 2SO 4Meter) chromyl sodium bisulfate, and used as the oxidation absorption liquid, with pump with this oxidation absorption liquid with 10m 3The flow of/h is of a size of from the cat head input In the absorption tower of 1000mm * 10000mm.To dewater from the calcining tails dedusting in limekiln, use air blast with 20000m 3The flow of/h passes into the absorption tower at the bottom of tower.In described limekiln calcining tail gas, the content of carbon dioxide is 38 volume %, and the content of sulfur dioxide is 2.5 volume %.Make oxidation absorption liquid and limekiln calcining tail gas at normal temperatures and pressures in the absorption tower counter current contacting form oxidation and absorb and finish liquid, simultaneously at the bottom of tower with pump with 50m 3The flow of/h is finished liquid with the oxidation absorption and is recycled to cat head.Liquid is finished in the oxidation absorption taken out at the bottom of tower, the carbon dioxide that has removed sulfur dioxide is then discharged from cat head.The oxidation absorption is finished liquid and is comprised 17.4 % by weight chromium sulfates, 1.7 % by weight niter cakes and 3.1 % by weight sulfuric acid.The content of carbon dioxide is 38.9 volume % in the described carbon dioxide.The removal efficiency of the sulfur dioxide in the limekiln calcining tail gas is 96%.
At the bottom of tower, take out 10m 3Oxidation absorbs finishes liquid, and uses 1.5m 3Trioctylphosphine amine extraction 3 times, chromic content is 101.0gL in the raffinate -1(with Cr 2O 3Meter).Described raffinate is delivered to the chromium powder manufacturing shop as making tanning with the feedstock pump of chromium powder.
Use 2.5m 3Water is with 2m 3Extract is stripped 3 times, obtains 2.9m 3Dilute sulfuric acid, its acid number are 135.7gL -1(with H 2SO 4Meter).This dilute sulfuric acid is used for the reduction of chromate waste water as acidulant.
Embodiment 3
The melting niter cake that will generate in Production By Sulfuric Acid Process chromic anhybride process is soluble in water, and the acquisition content of 6-valence Cr ions is 144gL -1(with Na 2Cr 2O 72H 2The O meter), niter cake content is that 7.8 % by weight and acid number are 453gL -1(with H 2SO 4Meter) chromyl sodium bisulfate, and used as the oxidation absorption liquid, with pump with this oxidation absorption liquid with 10m 3The flow of/h is of a size of from the cat head input In the absorption tower of 1000mm * 10000mm.To dewater from the calcining tails dedusting in limekiln, use air blast with 20000m 3The flow of/h passes into the absorption tower at the bottom of tower.In described limekiln calcining tail gas, the content of carbon dioxide is 30 volume %, and the content of sulfur dioxide is 2.7 volume %.Make oxidation absorption liquid and limekiln calcining tail gas at normal temperatures and pressures in the absorption tower counter current contacting form oxidation and absorb and finish liquid, simultaneously at the bottom of tower with pump with 50m 3The flow of/h is finished liquid with the oxidation absorption and is recycled to cat head.Liquid is finished in the oxidation absorption taken out at the bottom of tower, the carbon dioxide that has removed sulfur dioxide is then discharged from cat head.The oxidation absorption is finished liquid and is comprised 13.5 % by weight chromium sulfates, 2.2 % by weight niter cakes and 1.6 % by weight sulfuric acid.The content of carbon dioxide is 30.1 volume % in the described carbon dioxide.The removal efficiency of the sulfur dioxide in the limekiln calcining tail gas is 95%.
At the bottom of tower, take out 8m 3Oxidation absorbs finishes liquid, and uses 1.5m 3Three iso-octyl amine extractions 3 times, chromic content is 58.7gL in the raffinate -1(with Cr 2O 3Meter).Described raffinate is delivered to the chromium powder manufacturing shop as making tanning with the feedstock pump of chromium powder.
Use 2m 3Water is with 1.8m 3Extract is stripped 3 times, obtains 2.2m 3Dilute sulfuric acid, its acid number are 70.1gL -1(with H 2SO 4Meter).This dilute sulfuric acid is used for the reduction of chromate waste water as acidulant.

Claims (10)

1. method with the sulfur dioxide removal in the Industrial Stoves tail gas, described method comprises: the chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed.
2. according to claim 1 method, wherein said chromyl sodium bisulfate comprises with Na 2Cr 2O 72H 2O counts the Cr VI of 5-60 % by weight and the niter cake of 1-15 % by weight, and its acid number is with H 2SO 4Count 50-800g/l.
3. according to claim 1 method wherein is dissolved in the water by the melting niter cake that will generate in Production By Sulfuric Acid Process chromic anhybride process and Separation of Solid and Liquid obtains chromyl sodium bisulfate as the oxidation absorption liquid.
4. a comprehensive utilization is in the method for chromyl sodium bisulfate and the Industrial Stoves tail gas of Production By Sulfuric Acid Process chromic anhybride byproduct in process, and described method comprises:
Chromyl sodium bisulfate at Production By Sulfuric Acid Process chromic anhybride byproduct in process is contacted with Industrial Stoves tail gas as the oxidation absorption liquid, thus the oxidizing sulfur dioxide in the Industrial Stoves tail gas is removed, and the acquisition carbon dioxide is finished liquid with the oxidation absorption that comprises chromium sulfate, niter cake and sulfuric acid; With
Carbon dioxide is used for roasting chromite prepares sodium chromate, therein the sodium chromate alkaline solution is neutralized; Perhaps carbon dioxide is used for carbonizatin method and produces sodium dichromate, with therein with chromium acid sodium solution carbonization or pre-carbonization.
5. according to claim 4 method, wherein said chromyl sodium bisulfate comprises with Na 2Cr 2O 72H 2O counts the Cr VI of 5-60 % by weight and the niter cake of 1-15 % by weight, and its acid number is with H 2SO 4Count 50-800g/l.
6. according to claim 4 method wherein is dissolved in the water by the melting niter cake that will generate in Production By Sulfuric Acid Process chromic anhybride process and Separation of Solid and Liquid obtains chromyl sodium bisulfate as the oxidation absorption liquid.
7. each method according to claim 4-6, described method comprise also that separation of oxygenated absorbs to be finished liquid and obtains tanning with chromium powder and dilute sulfuric acid, and described dilute sulfuric acid is used for the reduction of chromate waste water as acidulant.
8. each method according to claim 4-6, described method also comprise utilizes three (C 8-10Alkyl) amine absorbs oxidation and finishes liquid and carry out extract and separate, obtain thus the vitriolated extract of bag and comprise chromium sulfate and the raffinate of niter cake, and the raffinate that will describedly comprise chromium sulfate and niter cake is as the raw material of making tanning and use chromium powder.
9. according to claim 8 method is wherein utilized three iso-octyl amine that oxidation is absorbed and is finished liquid and carry out extract and separate.
10. according to claim 8 or 9 method, described method comprises that also the water vitriolated extract of bag of stripping obtains dilute sulfuric acid, and it is used for the reduction of chromate waste water as acidulant.
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