CN105600805A - Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process - Google Patents
Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process Download PDFInfo
- Publication number
- CN105600805A CN105600805A CN201610038217.0A CN201610038217A CN105600805A CN 105600805 A CN105600805 A CN 105600805A CN 201610038217 A CN201610038217 A CN 201610038217A CN 105600805 A CN105600805 A CN 105600805A
- Authority
- CN
- China
- Prior art keywords
- resin
- ammonium
- desulfurizing agent
- ammonium sulfate
- purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating and purifying ammonium sulfate from by-product solution in a flue gas desulfurizing agent regeneration process. The method includes: filling NH4+ type cation exchange resin into a cation exchange column by a wet process, and allowing sodium bicarbonate regeneration by-product mixed solution to pass through a resin bed layer to collect sodium bicarbonate outflow liquid and ammonium sulfate at the bottom of the column; using dilute sulphuric acid for acidizing the outflow liquid, and drying to obtain ammonium sulfate, so that separation and purification are finished; using deionized water, ammonium bicarbonate solution and deionized water for sequentially eluting failed ion exchange resin in the exchange column to realize regeneration for obtain NH4+ type resin. By the ion exchange resin, high-purity ammonium sulfate is obtained by high-efficiency conversion, purification and acidification of the sodium bicarbonate regeneration by-product mixed solution; the loading resin is recyclable after regeneration, the resin regeneration outflow liquid can also serve as a desulfurizing agent, discharging of waste residues and waste liquid is avoided, technical environment friendliness, economy and utilization rate are increased, and a reasonable approach is provided for recovery.
Description
Technical field
The invention belongs to industrial wastewater and utilize technical field, be specifically related to a kind of from fume desulfurizing agent regenerative process by-product solutionThe method of separation and purification ammonium sulfate.
Background technology
The atmosphere pollution of current China is day by day serious, and as maximum in the world coal production state and country of consumption, sulfur dioxide (SO2) emissions are totalAmount is in world's umber one, and under this background, flue gas desulfurization technique has obtained fast development in recent years, but a large amount of desulfurizationAccessory substance is also following, and for traditional limestone-gypsum method, China only just produces 5,230 ten thousand tons of desulfurated plasters for 2010,Desulfurated plaster comprehensive utilization is poor, and present stage is mainly to abandon that to stack be main, has both wasted land resource, produces again environmental pollution.Therefore it is instant in face of chemical industry and environmentalist of pendulum that the accessory substance, desulphurization denitration process being produced is processedTask.
Sodium acid carbonate sulfur method is faster than traditional desulfurization method of limestone-gypsum rate high (approaching 100% removal efficiency), reaction rate,Alkali utilization rate is high, and can remove the heavy metal such as nitrogen oxide and mercury simultaneously, Tongji University's Dongmei SUN " sodium acid carbonate desulfurization andThe screening of its optimal conditions is inquired into " and TimothyC.Keener at " StudyoftheReactionofSO2withNaHCO3andNa2CO3" in all mention NaHCO3Under different shape, generally there is good desulfurized effect, have before very big exploitationOn the way. But face two large problems, the processing problem of cost of material height and accessory substance, has restricted sodium acid carbonate absorbent in desulfurization workDevelopment in industry, does not at utmost bring its advantage into play. NaHCO3Flue gas desulfurization main chemical reactions is:2NaHCO3+SO2+1/2O2→Na2SO4+2CO2+H2O，2NaHCO3→Na2CO3+CO2+H2O，Na2CO3+SO2+1/2O2→Na2SO4+2CO2。
In order to reduce cost and by-product contamination, " TheAirbornProcessTM" spent ten years and worked out a whole set ofSodium acid carbonate removes SO2(US005980848A, US7393378B2), sodium acid carbonate regeneration (US6475458B) and againPatent that raw accessory substance fertilizer has been purified the technology of (US006106796A) SEPARATE APPLICATION, and in U.S.'s Gent Kentucky State(5MW of Airborn company power plant demonstration project), the Wyoming State (JimBridger power plant) and Haier of West Germany cloth are grand(Solvary power plant) and other places drops into application. Sodium acid carbonate regenerative process main chemical reactions equation is:NH4HCO3+Na2SO4→(NH4)2SO4+NaHCO3↓, with cheap carbonic hydroammonium, more expensive sodium acid carbonate is regeneratedOut, NaHCO3In residual solution after crystallization, contain Na2SO4、(NH4)2SO4、NH4HCO3With a small amount of NaHCO3, thisIf kind of waste water directly discharge will cause serious water pollution, Airborn by this waste water through dilute sulfuric acid acidifying gained ammonium sulfate withThe two salting liquids of sodium sulphate, consider that again the economic worth of sodium sulphate in this waste water is limited, thus this waste water is carried out to separating-purifying,Obtain high-purity sulfuric acid ammonium, ammonium sulfate can be used as nitrogenous fertilizer, ore floatation, metal recovery, production refractory material etc., thereby can obtainEconomic benefit that must be larger, through 6 years (1990～1996) time process optimizations, its utilization Steppecd crystallization was pure by ammonium sulfateDegree brings up to 99% from 60%, and the sodium sulphate of separating turns back to the sodium acid carbonate regeneration stage again. This method is to Control system resolutionRequire high, expend heat energy, crystallization and sweating speed and be difficult for effectively controlling, recyclability is not strong.
Summary of the invention
For overcoming the problems of the prior art, the object of this invention is to provide one selectively good, can be recycled, environmental pollutionLess, be suitable for the method for separation and purification ammonium sulfate from fume desulfurizing agent regenerative process by-product solution that suitability for industrialized production, cost are low.
To achieve these goals, the present invention adopts following technical scheme:
A method for separation and purification ammonium sulfate from fume desulfurizing agent regenerative process by-product solution, by NH4 +Type cation exchangeResin adopts wet method to be filled in cation exchange column, under room temperature, fume desulfurizing agent regenerative process accessory substance mixed solution is passed throughResin bed, the Na in the accessory substance mixed solution that fume desulfurizing agent regenerative process produces+With the NH on resin4 +There is exchange anti-Should, collect post underflow fluid, with the Na in efflux+Concentration reaches 5mg/L for collecting terminal; By the efflux process of collectingSulfuric acid acidation to pH value be 4～5 and dry after, obtain ammonium sulfate, complete separation and purification.
Described NH4 +Type cationic ion-exchange resin is for containing sulfonic resin.
Described is gel type cation exchanger resin SepliteLSI-010, large pores cation exchange resin containing sulfonic resinAmberliteFPC22Na or Amberlite252Na.
Described fume desulfurizing agent regenerative process accessory substance mixed solution is 2～8BV/h by the flow velocity of resin bed.
By the NH after losing efficacy4 +Type cationic ion-exchange resin first with deionized water wash to efflux pH value be 7～9, then use carbonAcid hydrogen ammonium salt solution, ammonium chloride solution or ammonium sulfate drip washing resin, finally with deionized water wash to efflux pH value be 7～9, obtain NH4 +Type cationic ion-exchange resin, NH4 +Type cationic ion-exchange resin can reuse.
The molar concentration of described ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1～2mol/L, ammonium bicarbonate soln,The volume of ammonium chloride solution or ammonium sulfate is 3～5BV.
By the NH after losing efficacy4 +When type cationic ion-exchange resin first washs by deionized water, the flow velocity of deionized water used is 6～8BV/h。
The flow velocity of described ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1.5～2BV/h.
Compared with prior art, the beneficial effect that the present invention has is as follows: the present invention at room temperature, uses NH4 +Type cation exchangeResin carries out ion-exchange reactions and efflux to fume desulfurizing agent regenerative process by-product solution, and to be acidified to pH value be 4～5 alsoDry, obtain high-purity sulphuric acid ammonium, have easy, the advantage that purification efficiency is high, resin can repeat regeneration, and resin againRaw process streams fluid also can continue to serve as desulfurizing agent, and the ammonium sulfate purity obtaining by the method reaches more than 97%, has higherActual application value, solved the difficulty behaviour that in prior art, sodium acid carbonate exists in processing as desulfurizer regeneration process accessory substanceControl, the problem that energy consumption is too large, the present invention greatly reduces production cost, has made up the high shortcoming of sodium acid carbonate method desulphurization cost,Can not introduce again other foreign ion, reduce water pollution, high, selective without waste residue and liquid discharge, comprehensive utilization of resources rateGood, the green economy of whole method is good, provides rational approach for reclaiming valuable industry and product for agriculture, more carbonic acidHydrogen sodium method provides in the extensive use in flue gas desulfurization field may. For the mixed liquor that contains ammonium ion and sodium ion in solution,Anion is other ion, such as carbanion, chlorion, bicarbonate radical etc., can adopt equally the method in the present inventionPurify.
Further, the resin after ion-exchange can carry out recycling utilization with ammonium bicarbonate soln or other ammonium salt solution,Regenerative process efflux can continue to serve as desulfurizing agent or recycling, and resin repeat usage is high.
Further, if use ammonium sulfate regenerating resin, efflux is two salt sodium sulphate and ammonium sulfate mixed solution, this mixingSolution can return to ion-exchange again and acidifying obtains ammonium sulfate, and regeneration use ammonium sulfate come to desulfurizing byproduct solution fromThe ammonium sulfate obtaining after son exchange acidifying. This is also a circulation.
Brief description of the drawings
Fig. 1 is the schematic diagram that carries out exchange adsorption on ion exchange resin.
Detailed description of the invention
Adopt the mode of specific embodiment to explain particularly the present invention below, but the present invention is not limited to embodiment. Sulphur in the present inventionThe concentration of acid is 0.1mol/L.
The present invention includes following steps:
1) by NH4 +Type cationic ion-exchange resin adopts wet method to be filled in cation exchange column, under room temperature, by fume desulfurizing agent againRaw process by-product solution (be sodium acid carbonate desulfurization regeneration accessory substance mixed solution, Na2SO4、(NH4)2SO4、NH4HCO3With a small amount of NaHCO3) pass through resin bed, Na in fume desulfurizing agent regenerative process by-product solution with the flow velocity of 2～8BV/h+NH with combination on resin4 +There is exchange reaction, collect post underflow fluid, with the Na in efflux+Concentration reaches 5mg/L for wholePoint, stops collecting.
2) in efflux, comprise ammonium sulfate and carbonic hydroammonium, it is 4～5 also that the efflux of collection is acidified to pH value through dilute sulfuric acidAfter dry, obtain ammonium sulfate, complete separation and purification; Wherein, BV is resin volume.
3) adopt wet method to be filled in exchange column the cationic ion-exchange resin after losing efficacy, first adopt deionized water with 6～8BV/hWash to efflux pH value be 7～9, the ammonium bicarbonate soln that is then 1～2mol/L by 3～5BV, molar concentration is with 1.5～2The speed drip washing resin of BV/h, finally washs to efflux pH value as 7～9 taking 6～8BV/h by deionized water, obtains NH4 +TypeCationic ion-exchange resin, described NH4 +The contained cation exchange groups of type cationic ion-exchange resin, for containing sulfonic resin, contains benzene sulfonic acid baseResin can use equally.
Described with ammonium bicarbonate soln drip washing resin, efflux is that sodium acid carbonate and carbonic hydroammonium mixed solution can continue to serve as flue gasDesulfurizing agent. The ammonium salts such as ammonium bicarbonate soln also can be used ammonium chloride solution, ammonium sulfate replace, but now, efflux is exactly chlorineSalt or sulfate liquor, also recyclable conversion recycling. The object that adopts sulfuric acid in the present invention is acidifying, and its concentration is unrestricted.
The present invention is described in detail below:
The first step, the type selecting of resin: according to the characteristic of ion exchange resin, then in conjunction with the current sodium acid carbonate desulfurization that needs purifyingThe essence & characteristics of regeneration accessory substance mixed solution, selects storng-acid cation exchange resin, in conjunction with self system and resinOperation parameter and performance, the NH of final choice4 +Type cationic ion-exchange resin is to be the tree of sulfonic group or benzene sulfonic acid base containing cation exchange groupsFat.
Second step, transforms purification ammonium sulfate: utilize NH4 +Na in type cationic ion-exchange resin and solution+Carry out exchange reaction, andBe 4～5, dryly obtain highly purified ammonium sulfate thereby efflux is acidified to pH, concrete, by NH4 +Type sunIon exchange resin wet method is filled in cation exchange column, under room temperature, sodium acid carbonate desulfurization regeneration byproduct in process thing is mixedSolution passes through resin bed with the flow velocity of 2～8BV/h, thus the Na in liquid phase+Move to resin particle surface from liquid phase main body,And with resin on the NH of combination4 +There is exchange reaction, the exchanged NH getting off4 +Be diffused into liquid phase main body, only make in solutionThere is NH4 +. Whole exchange process had both occurred in resin surface and had also occurred in resin inside, and followed equivalent exchange principle, reactionFormula is 2R-NH4+Na2SO4→2R-Na+(NH4)2SO4，R-NH4+NaHCO3→R-Na+NH4HCO3. ExchangeFig. 1 is shown in by the schematic diagram of absorption, in ion exchange process, is connected to the merit on the changeless skeleton in ion exchange resinThe ammonium ion that energy base dissociation goes out exchanges with sodium ion free in solution, and whole exchange process is followed equivalent exchange principle,And all there is ion exchange process on resin particle surface and inside, thus in solution, the amount of ammonium ion increases, at the bottom of collecting postAmmonium sulfate and carbonic hydroammonium efflux. Under normal circumstances, the speed of Liquid film diffusion or particle diffusion determines the general speed of ion-exchange.
Finally press formula Q=(C-C0) V/W converses the ion exchange capacity of ion exchange resin under fixed mass.
In formula: Q-Na+Exchange capacity;
C0NH in-solution4 +Initial concentration (mg/L);
NH in C-exchange current fluid4 +Concentration (mg/L);
V-effluent volume (L);
The quality (g) of W-separation and purification institute spent ion exchange resin;
The 3rd step, the transition of resin: the first resin that step 2 is transformed to the rear gained of purifying adopts wet method to be filled in exchange column,Adopt deionized water taking the flow velocity washing resin of 6～8BV/h to efflux pH value as 7～9, then adopt volume 3～5BV,Molar concentration be the ammonium bicarbonate soln of 1～2mol/L with the flow velocity drip washing resin of 1.5～2BV/h, sodium type resin is converted toNH4+ type cationic ion-exchange resin, deionized water taking the flow velocity washing resin of 6～8BV/h to efflux pH value as 7～9, willObtain NH4 +It is for subsequent use that type storng-acid cation exchange resin is put into closed container.
The 4th step: acidifying the dry ammonium sulfate that obtains: the ammonium sulfate that step 2 is obtained and carbonic hydroammonium efflux are through rare sulphurAcid be acidified to pH value be 4～5 and dry after, obtain ammonium sulfate, complete separation and purification. Acidifying is placed on to by-product solution ionAfter exchange, can greatly increase Na+With NH4 +Between exchange capacity. According to " mensuration (the formaldehyde of nitrogen content in ammonium sulfate fertilizerMethod) " detect the purity of ammonium sulfate. The ammonium sulfate purity obtaining is higher than 97%.
Be elaborated below by specific embodiment. Fume desulfurizing agent regenerative process by-product solution in embodiment 1～5For sodium acid carbonate regenerative process by-product solution. In embodiment, all adopting mass concentration is 2%, Na2SO4、(NH4)2SO4、NH4HCO3And NaHCO3The molar concentration rate mixed solution that is 2:4:2:1, ion-exchange column volume is 120mL.
Embodiment 1:
1) adopt wet method to be filled in exchange column gel type cation exchanger resin SepliteLSI-010, first adopt deionizationWater to efflux pH value as 7～9, is then 1mol/L by volume 4BV, molar concentration taking the flow velocity washing resin of 6BV/hAmmonium bicarbonate soln with 1.5BV/h flow velocity drip washing resin, last again by deionized water with the flow velocity washing resin of 6BV/h to streamFluid pH value is 7～9, obtains NH4 +Type cationic ion-exchange resin.
2) by NH4 +Type cationic ion-exchange resin adopts wet method to be filled in cation exchange column, under room temperature, by fume desulfurizing agentRegenerative process by-product solution is passed through resin bed, Na with the flow velocity of 3BV/h+NH with combination on resin4 +There is exchange reaction,Ammonium sulfate and carbonic hydroammonium efflux at the bottom of collection post, with the Na in efflux+It is terminal that concentration reaches 5mg/L, stop collecting,The ion exchange capacity Q that determines SepliteLSI-010 resin is 20.1mg/g, and the efflux of collection is acidified to through dilute sulfuric acidPH value be 4～5 and dry at 55 DEG C in vacuum drying chamber after, recording ammonium sulfate purity is 98.2%.
Embodiment 2: amplification test
1) adopt wet method to be filled in exchange column large pores cation exchange resin AmberliteFPC22Na, first adopt and goIonized water to efflux pH value as 7～9, then adopts volume 5BV, molar concentration to be taking the flow velocity washing resin of 8BV/hThe ammonium bicarbonate soln of 1.5mol/L, with 1.5BV/h flow velocity drip washing resin, is finally washed with the flow velocity of 8BV/h by deionized water againWashing resin to efflux pH value is 7～9, obtains NH4 +Type cationic ion-exchange resin.
2) (be NH to the wet resin of each filling 120mL in two exchange columns respectively4 +Type cationic ion-exchange resin), then by twoIndividual exchange column is together in series, and regeneration accessory substance mixed solution is passed through to resin bed with the flow velocity of 2BV/h, when second exchange columnNa in efflux+When concentration reaches 5mg/L, shut-down operation, regenerates to the resin in two pillars, beginning second batchPurifying experiment, the single batch for the treatment of capacity to regeneration accessory substance mixed solution is 20BV left and right, determines first batch of FPC22NaThe ion exchange capacity Q of resin is 23.8mg/g, the ammonium sulfate of collection and ammonium bicarbonate soln is acidified to pH through dilute sulfuric acid be4～5 and dry after, the ammonium sulfate purity that records first batch is that the exchange capacity Q of 99.2%, the second batch is 21.6mg/g, sulphurAcid ammonium purity is that the exchange capacity Q of 98.2%, the three batch is 20.8mg/g, and ammonium sulfate purity is the friendship of 97.5%, the four batchThe amount of changing Q is 19.5mg/g, and ammonium sulfate purity is that the exchange capacity Q of 97%, the five batch is 19.1mg/g, and ammonium sulfate purity is96.5%, amplification test result shows, resins exchange rate is high, and gained ammonium sulfate purity is high, and absorption property is stable, after regeneration is processedResin adsorption performance ideal, keep higher adsorption rate.
Embodiment 3:
1) adopt wet method to be filled in exchange column large pores cation exchange resin AmberliteFPC22Na, first adopt and goIonized water is taking the flow velocity washing resin of 6BV/h to efflux pH value as 7～9, and then adopting volume is 3BV, molar concentrationFor the ammonium sulfate of 2mol/L is with 1.5BV/h flow velocity drip washing resin, the last flow velocity washing with 6BV/h by deionized water againResin to efflux pH value is 7～9, obtains NH4 +Type cationic ion-exchange resin.
2) by NH4 +Type cationic ion-exchange resin adopts wet method to be filled in cation exchange column, under room temperature, by fume desulfurizing agentRegenerative process regeneration accessory substance mixed solution passes through resin bed, Na with the flow velocity of 8BV/h+NH with combination on resin4 +OccurExchange reaction, collects post underflow fluid, with the Na in efflux+It is terminal that concentration reaches 5mg/L, determines AmberliteFPCThe ion exchange capacity Q of 22Na resin is 19.1mg/g, and the ammonium sulfate of collection and ammonium bicarbonate soln are acidified to through dilute sulfuric acidPH is 4～5, and after being dried in 55 DEG C of vacuum drying chambers, recording ammonium sulfate purity is 97.3%.
Embodiment 4:
1) by large pores cation exchange resin Amberlite252Na adopt wet method be filled in exchange column, first adopt go fromSub-water to efflux pH value as 7～9, is then that 1.5mol/L, volume are by molar concentration taking the flow velocity washing resin of 7BV/hThe ammonium chloride solution drip washing resin that 5BV, flow velocity are 1.8BV/h, the last flow velocity washing tree with 6BV/h by deionized water againFat to efflux pH value is 7～9, obtains NH4 +Type cationic ion-exchange resin.
2) by NH4 +Type cationic ion-exchange resin adopts wet method to be filled in cation exchange column, under room temperature, by fume desulfurizing agentRegenerative process regeneration accessory substance mixed solution passes through resin bed, Na with the flow velocity of 6BV/h+NH with combination on resin4 +OccurExchange reaction, collects post underflow fluid, with the Na in efflux+It is terminal that concentration reaches 5mg/L, determines AmberliteThe ion exchange capacity Q of F252Na resin is 19.6mg/g, by the ammonium sulfate of collecting and the acidifying of ammonium bicarbonate soln process dilute sulfuric acidTo pH be 4～5, dry in 55 DEG C of vacuum drying chambers after, recording ammonium sulfate purity is 97.6%.
For the mixed liquor that contains ammonium ion and sodium ion in solution, anion is other ion, such as carbanion, chlorine fromSon, bicarbonate radical etc., can adopt the method in the present invention to purify equally.
The present invention is in order to solve the processing problem of existing sodium acid carbonate desulfur technology cost of material height and accessory substance, for sodium acid carbonateRegenerative process accessory substance mixed solution, transforms purification to the ammonium sulfate in mixed solution, and introduces first ion exchange resinSodium acid carbonate regenerative process accessory substance mixed solution is carried out to purification process, and obtained desirable effect, thus the high-purity of obtainingAmmonium sulfate, developed a kind of selectively good, the rate of recovery is high, can be recycled, low in the pollution of the environment, the sulphur that is suitable for suitability for industrialized productionAcid ammonium ion exchanges preparation technology, has improved the green economy of whole sodium acid carbonate sulfur removal technology.
Claims (8)
1. a method for separation and purification ammonium sulfate from fume desulfurizing agent regenerative process by-product solution, is characterized in that, willNH4 +Type cationic ion-exchange resin adopts wet method to be filled in cation exchange column, under room temperature, by fume desulfurizing agent regenerative process pairProduct mixed solution passes through resin bed, the Na in the accessory substance mixed solution that fume desulfurizing agent regenerative process produces+On resinNH4 +There is exchange reaction, collect post underflow fluid, with the Na in efflux+Concentration reaches 5mg/L for collecting terminal; WillCollect efflux through sulfuric acid acidation to pH value be 4～5 and be dried after, obtain ammonium sulfate, complete separation and purification.
According to claim 1 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, described NH4 +Type cationic ion-exchange resin is for containing sulfonic resin.
According to claim 2 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, described containing sulfonic resin be gel type cation exchanger resin SepliteLSI-010, macroporous type sun fromSub-exchange resin AmberliteFPC22Na or Amberlite252Na.
According to claim 1 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, described fume desulfurizing agent regenerative process accessory substance mixed solution is 2～8BV/h by the flow velocity of resin bed.
According to claim 1 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, by the NH after losing efficacy4 +Type cationic ion-exchange resin first with deionized water wash to efflux pH value be 7～9, then use ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate drip washing resin, finally wash to efflux by deionized waterPH value is 7～9, obtains NH4 +Type cationic ion-exchange resin, NH4 +Type cationic ion-exchange resin can reuse.
According to claim 5 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, the molar concentration of described ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1～2mol/L,The volume of ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 3～5BV.
According to claim 5 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, by the NH after losing efficacy4 +When type cationic ion-exchange resin first washs by deionized water, deionized water usedFlow velocity is 6～8BV/h.
According to claim 5 a kind of from fume desulfurizing agent regenerative process by-product solution the side of separation and purification ammonium sulfateMethod, is characterized in that, the flow velocity of described ammonium bicarbonate soln, ammonium chloride solution or ammonium sulfate is 1.5～2BV/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038217.0A CN105600805B (en) | 2016-01-20 | 2016-01-20 | A kind of method that ammonium sulfate is isolated and purified in the regenerative process by-product solution from fume desulfurizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038217.0A CN105600805B (en) | 2016-01-20 | 2016-01-20 | A kind of method that ammonium sulfate is isolated and purified in the regenerative process by-product solution from fume desulfurizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105600805A true CN105600805A (en) | 2016-05-25 |
| CN105600805B CN105600805B (en) | 2017-06-16 |
Family
ID=55981235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610038217.0A Expired - Fee Related CN105600805B (en) | 2016-01-20 | 2016-01-20 | A kind of method that ammonium sulfate is isolated and purified in the regenerative process by-product solution from fume desulfurizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105600805B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416868A (en) * | 2017-06-15 | 2017-12-01 | 山东大正节能环保科技有限公司 | A kind of preparation technology of sodium bicarbonate and ammonium sulfate Chemical Mixed Fertilizer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS524500A (en) * | 1975-07-01 | 1977-01-13 | Asahi Chem Ind Co Ltd | Recoverring method of ammonium sulfate from waste solution |
| JPS5394447A (en) * | 1977-01-31 | 1978-08-18 | Mitsui Eng & Shipbuild Co Ltd | Method of traeting waste water containing ammonia nitrogen |
| CN87103546A (en) * | 1987-05-18 | 1987-11-04 | 黄圣恒 | From diluted thioamine liquid, reclaim the method for solid ammonium sulfate |
| CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
| CN101367568A (en) * | 2008-09-19 | 2009-02-18 | 广西大学 | Process for the separation of strong-acid cation exchange fibre of indium and cadmium |
| CN103420448A (en) * | 2013-08-22 | 2013-12-04 | 张家港燎原环保科技有限公司 | Thiosulfate removing method for coke oven gas desulfuration liquid waste using ion exchange resin |
-
2016
- 2016-01-20 CN CN201610038217.0A patent/CN105600805B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS524500A (en) * | 1975-07-01 | 1977-01-13 | Asahi Chem Ind Co Ltd | Recoverring method of ammonium sulfate from waste solution |
| JPS5394447A (en) * | 1977-01-31 | 1978-08-18 | Mitsui Eng & Shipbuild Co Ltd | Method of traeting waste water containing ammonia nitrogen |
| CN87103546A (en) * | 1987-05-18 | 1987-11-04 | 黄圣恒 | From diluted thioamine liquid, reclaim the method for solid ammonium sulfate |
| CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
| CN101367568A (en) * | 2008-09-19 | 2009-02-18 | 广西大学 | Process for the separation of strong-acid cation exchange fibre of indium and cadmium |
| CN103420448A (en) * | 2013-08-22 | 2013-12-04 | 张家港燎原环保科技有限公司 | Thiosulfate removing method for coke oven gas desulfuration liquid waste using ion exchange resin |
Non-Patent Citations (1)
| Title |
|---|
| 曾庆华: "离子交换法制备纯硫代硫酸铵", 《化工技术与开发》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416868A (en) * | 2017-06-15 | 2017-12-01 | 山东大正节能环保科技有限公司 | A kind of preparation technology of sodium bicarbonate and ammonium sulfate Chemical Mixed Fertilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105600805B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103303877B (en) | Many sources of the gas low concentration SO 2smoke comprehensive reclaims acid-making process flow process | |
| CN102489132B (en) | Novel dual-alkali desulfurization method for removal of sulfur dioxide from flue gas and generation of elemental sulfur as byproduct | |
| CN107774082B (en) | Method and device for flue gas desulfurization | |
| CN106669361A (en) | Method for production of sulfuric acid by flue gas desulfurization and for sulfuric acid purification and device thereof | |
| CN102101010A (en) | Electrolysis circulating flue gas desulfurization method utilizing reclamation semidry method | |
| CN107311350A (en) | A kind of recycling treatment process of thermal power plant desulfurization wastewater | |
| CN105498539B (en) | A kind of method for recycling of fume desulfurizing agent | |
| CN105597512B (en) | A kind of renovation process of fume desulfurizing agent | |
| CN105645514B (en) | The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process | |
| CN102895845A (en) | Ionic liquid absorbent and preparation method and application thereof | |
| CN100482596C (en) | Method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously | |
| CN113800494B (en) | Method for selectively recycling aluminum from acid leaching solution of waste lithium iron phosphate battery material | |
| CN103224246B (en) | Chemical gypsum-to-ammonium sulfate reaction slurry concentration, waste heat recovery and waste ammonia recovery method | |
| CN102658011A (en) | Method for concentrating, converting, recovering and processing light concentration SO2 (sulfur dioxide) flue gas | |
| CN101979130A (en) | Method for removing hydrogen sulfide from industrial gas in recycling way | |
| CN105600805A (en) | Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process | |
| CN105964127A (en) | SO2 absorbing and converting technological method | |
| CN113769564A (en) | Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof | |
| CN103332751B (en) | Ferrous sulfate method of comprehensive utilization | |
| CN106669360A (en) | Method and apparatus for flue gas desulfurization and sulfuric acid production | |
| CN103553078B (en) | Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization | |
| CN102728205A (en) | Method for flue gas desulfurization by sodium-calcium double alkali method | |
| CN204911189U (en) | Device of hydrogen phosphate in desorption yellow phosphoric tail gas | |
| CN102188959A (en) | Regeneration method for saturated zeolite absorbing ammonia nitrogen in sewage | |
| CN202700350U (en) | Device for desulfurizing flue gas by using sodium-calcium dual alkali method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170616 Termination date: 20220120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |