CN101659422B - Ammonium salt solution concentration method - Google Patents
Ammonium salt solution concentration method Download PDFInfo
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- CN101659422B CN101659422B CN2009103080007A CN200910308000A CN101659422B CN 101659422 B CN101659422 B CN 101659422B CN 2009103080007 A CN2009103080007 A CN 2009103080007A CN 200910308000 A CN200910308000 A CN 200910308000A CN 101659422 B CN101659422 B CN 101659422B
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- ammonium salt
- ammonium
- salt solution
- sulfuric acid
- dehydration
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Abstract
The invention relates to an ammonium salt solution concentration method which mainly comprises the following technological processes: ammonium salt solution is added with dehydrated aluminum ammonium sulfate (potassium) vitriol, heated up and dissolved; ammonium salt solution is cooled and crystallized to separate out aluminum ammonium sulfate (potassium) vitriol with crystal water which is crystallized and then concentrated; aluminum ammonium sulfate (potassium) vitriol is heated, dehydrated and recycled; and the concentrated ammonium salt solution is comprehensively utilized. The concentration method has the advantages of simple operation, environmental friendly, strong technological adaptability, low concentration cost, zero waste water discharge and the like.
Description
Technical field
The present invention relates to a kind of ammonium salt solution concentration method.
Background technology
The exploitation of ammonia nitrogenous wastewater treatment technology has become the emphasis and the focus of water pollution control engineering area research.Ammonia nitrogen waste water is mainly derived from industries such as metallurgy, chemical industry, and its ammonia nitrogen mainly is present in the waste water with the form of ammonium salt.Can remove effectively in the waste water there to be much the method for ammonium salt, as biological process, physics method, chemical method etc.At present domestic rare ammonium salt wastewater treatment method is mainly contained: carry out pre-treatment earlier, and then adopt activated sludge process; Or after film held back pre-concentration, revaporization concentrated, then crystallisation by cooling.Yet first film is held back pre-concentration, and revaporization concentrates, and then the running cost of crystallisation by cooling processing ammonium salt waste water is very high, uneconomical economically.This treatment process has theoretical Research Significance, but does not have actual application value.For the high density ammonium salt solution that enterprises such as ammonium nitrate factory, explosive factory, ammonium molybdate factory produce,, generally all be dilution discharge owing to also lack rational improvement method.Recently, also someone's method of adopting revaporization behind the electrodialysis pre-concentration to concentrate inhibition and generation fertilizer is come comprehensive regulation high density ammonium salt waste water.But not high for high density ammonium salt waste water electrodialysis concentrating efficiency, water a large amount of in the waste water can only be removed by evaporation concentration.What the ammonium salt solution evaporation concentration was with the most use at present is multiple-effect evaporator.Though concentrating, solution evaporation adopt the more common vaporizer of multiple-effect evaporator energy-conservation, but the investment of multiple-effect evaporator disposable apparatus is big, for many small businesss or the little enterprise of ammonium salt wastewater flow rate, ammonium salt waste water adopts multiple-effect evaporation to concentrate and administers, and has social benefit but not have economic benefit.In addition, for containing Cl
-Etc. the anionic ammonium salt waste water of corrodibility, the evaporating concentration process equipment corrosion is serious, and the waste gas that evaporation produces causes secondary pollution easily.
Summary of the invention
The object of the present invention is to provide a kind of method, can improve the ammonium salt solution thickening efficiency, reduce the thickening equipment investment, avoid the corrosion of ammonium salt solution concentration process equipment and the secondary pollution that evaporation waste gas causes, reduce a kind of ammonium salt solution crystallization concentration method of comprehensive regulation cost.
Technical scheme of the present invention is:
The present invention concentrates the traditional evaporation concentration of replacement with the enriching agent of dehydration sulfuric acid double salt as ammonium salt solution with crystallization, and specific implementation process may further comprise the steps: enriching agent adds the ammonium salt solution rising temperature for dissolving; The ammonium salt solution crystallisation by cooling is concentrated after separating out the sulfuric acid double salt crystal of being with crystal water; Sulfuric acid double salt crystal pyrolysis dewatering cycle is used; Concentrate the ammonium salt solution comprehensive utilization that obtains; The adding total amount of dehydration sulfuric acid double salt is 0.5～2.0 times of ammonium salt solution crystallization concentration process dehydration quality summation.
Described ammonium salt is meant one or more in ammonium chloride, ammonium nitrate, the ammonium sulfate.
Described ammonium salt solution is meant the solution or the waste water of unsaturated ammonium salt-containing under the room temperature.
Described dehydration sulfuric acid double salt is the Tai-Ace S 150 ammonium alum, Tai-Ace S 150 arcanite and the exsiccated ammonium alum that partly or entirely lose crystal water and in the potassium aluminium sulfate mixing alum one or more.
Described dehydration sulfuric acid double salt rising temperature for dissolving is 50～110 ℃ of stirrings dissolving in 0.2～2.0 hour in ammonium salt solution; Described cooling is that nature or pressure are cooled to room temperature; Sulfuric acid double salt crystal pyrolysis dehydration is to lose part or all of crystal water in 1～3 hour 80～280 ℃ of pyrolysis, and the dehydration sulfuric acid double salt returns the ammonium salt solution crystallization and concentrates and recycle.
It is that solution nature or pressure are cooled to the sulfuric acid double salt crystal that room temperature is separated out the band crystal water, seize the process that the water ammonium salt in the solution is concentrated after adding ammonium salt solution intensification stirring and dissolving by the dehydration sulfuric acid double salt that crystallization of the present invention concentrates.
Pyrolysis of the present invention dehydration is to make sulfuric acid double salt crystal block section that crystallization obtains or the process that all loses crystal water by heating.Sulfuric acid double salt after the dehydration returns the ammonium salt solution crystallization and concentrates and to recycle.
After the comprehensive utilization of described ammonium salt solution was meant that crystallization concentrates the ammonium salt solution that obtains and removes impurity such as aluminium through purification, further crystallisation by cooling got ammonium salt, or returns main technological cycle and use, or spraying drying is produced chemical fertilizer.
AlNH
4(SO
4)
2+12H
2O→AlNH
4(SO
4)
2·12H
2O↓
AlK(SO
4)
2+12H
2O→AlK(SO
4)
2·12H
2O↓
Specific embodiment of the invention process is:
The ammonium salt solution crystallization concentrates and mainly may further comprise the steps: the dehydration sulfuric acid double salt adds the ammonium salt solution rising temperature for dissolving, the sulfuric acid double salt crystal ammonium salt solution that crystallisation by cooling is separated out the band crystal water is concentrated, ammonium salt solution comprehensive utilization after concentrating, sulfuric acid double salt crystal thermal dehydration recycles, the relevant parameter of its technological process is: ammonium salt solution reaches predetermined concentration after the one or many crystallization concentrates, the adding total amount of dehydration sulfuric acid double salt is 0.5-2.0 a times of ammonium salt solution crystallization concentration process dehydration quality summation, the dehydration sulfuric acid double salt in ammonium salt solution 50～110 ℃ stir dissolving in 0.2～2.0 hour after, nature or force is cooled to crystallizing at room temperature and separates out the water that the sulfuric acid double salt crystal of band crystal water captures in the solution ammonium salt is concentrated; Filter, filtrate purification further is cooled to 10～10 ℃ of crystallizations and reclaims ammonium salts, or return main technological cycle and use, or spraying drying is produced chemical fertilizer after removing impurity such as aluminium; Lost part or all of crystal water in 80～280 ℃ of pyrolysis 1-3 of the sulfuric acid double salt crystal that filtration obtains hours, the dehydration sulfuric acid double salt that obtains returns the ammonium salt solution crystallization and concentrates and to recycle.
The present invention compares with existing technology and has the following advantages and effect:
Advantage of the present invention just is, the art breading thinking of contriver's conversion process waste water, no longer be to be used to have improved mode by existing technician, a technology of considering how to improve traditional evaporation concentration just ignorantly, from another angle, adopt the dehydration sulfuric acid double salt to grab the enriching agent of dehydration exsiccated ammonium alum (potassium) alum as ammonium salt solution, adopt crystallization to concentrate and replace traditional evaporation concentration, whole technology has been done new trial.The contriver joins in the ammonium salt solution after the intensification stirring and dissolving by utilizing dehydration exsiccated ammonium alum (potassium) alum, because of reducing, exsiccated ammonium alum (potassium) alum solubility with temperature sharply reduces, and the solubleness of exsiccated ammonium alum in ammonium salt solution (potassium) alum is much smaller than its solubleness in water, cooling back exsiccated ammonium alum (potassium) alum almost fully crystallization separate out, the water that seizes in the solution is concentrated ammonium salt.
The present invention makes whole technology not only can improve thickening efficiency effectively by conventional art being improved the breakthrough of thinking, also can reduce thickening equipment investment and running cost thereof, avoids the corrosion of concentration process equipment and the secondary pollution that evaporation waste gas causes.The present invention has easy and simple to handle, environmental friendliness, and Technological adaptability is strong, and concentrated cost is low, advantages such as wastewater zero discharge.
Embodiment
Below in conjunction with embodiment, the present invention is further described, following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
The sodium chloride solution (ammonium meta-vanadate crystalline mother solution) that 1000ml contains ammonium chloride 10wt% is heated to 85 ℃, stir and add 724g anhydrous slufuric acid aluminium ammonium alum powder, the dissolving postcooling is to room temperature (28 ℃), and 1364g Tai-Ace S 150 ammonium alum crystal is separated out in crystallization, obtains the ammonium chloride concentrated solution that concentration is about 28wt%; Concentrated solution further is cooled to-5 ℃ of NH that crystallization is separated out
4The Cl crystal returns and is used for the precipitation of extracting vanadium from stone coal liquid; NH
4The Cl crystalline mother solution is used for the stone coal sodium roasting nodulizing; 220 ℃ of dehydrations of Tai-Ace S 150 ammonium alum crystal retort furnace are returned the crystallization enrichment process after 2 hours and are recycled.
Embodiment 2
2.5m
3Contain ammonium nitrate 6wt% waste liquid and be heated to 75 ℃, stir and add 2075kg anhydrous slufuric acid aluminium ammonium alum powder, the dissolving postcooling is to room temperature (25 ℃), and 3803kg Tai-Ace S 150 ammonium alum crystal is separated out in crystallization, obtains the ammonium nitrate primary crystallization concentrated solution 634L that concentration is about 29wt%; 30 ℃ of dehydrations of Tai-Ace S 150 ammonium alum crystal 2 are after 1.5 hours, and pulverizing is used for the ammonium nitrate solution secondary crystal and concentrates; Ammonium nitrate primary crystallization concentrated solution is heated to 95 ℃, stir and add 400kg dehydration Tai-Ace S 150 ammonium alum powder, the dissolving postcooling is to room temperature (30 ℃), and 813kg Tai-Ace S 150 ammonium alum crystal is separated out in crystallization, obtains the ammonium nitrate secondary crystal concentrated solution that concentration is about 60wt% simultaneously; The secondary crystal concentrated solution adds ammoniacal liquor adjust pH 5.5 earlier, quantitatively adds Ba (NO again
3)
2Remove Al
3+And SO
4 2-After, return ammonium nitrate production master technology; Returning the crystallization enrichment process after the concentrated 30 ℃ of dehydrations of Tai-Ace S 150 ammonium alum crystal 2 that obtain of secondary crystal recycles.
Embodiment 3
2000ml contains the heavy crystalline mother solution of ammonium nitrate 12wt% ammonium molybdate acid and removes molybdenum post-heating to 80 ℃ through ion-exchange, the powder that obtains after exsiccated ammonium alum that stirring adding 700g extracting vanadium by acid leaching of stone coal forms and the dehydration of potassium aluminium sulfate mixing alum crystal, the dissolving postcooling is to room temperature (20 ℃), 1303g Tai-Ace S 150 ammonium alum crystal is separated out in crystallization, obtains the ammonium nitrate primary crystallization concentrated solution 370ml that concentration is about 30wt%; 210 ℃ of dehydrations of Tai-Ace S 150 ammonium alum crystal retort furnace are after 2.5 hours, and pulverizing is used for secondary crystal and concentrates; Ammonium nitrate primary crystallization concentrated solution is heated to 90 ℃, stirs to add 240g dehydration Tai-Ace S 150 ammonium alum powder, and the dissolving postcooling is to room temperature (30 ℃), and 473g Tai-Ace S 150 ammonium alum crystal is separated out in crystallization, obtains the ammonium nitrate secondary crystal concentrated solution that concentration is about 64wt%; The secondary crystal concentrated solution stirs and adds 47g anhydrous slufuric acid calcium powder, and spraying drying gets the ammonium nitrate fertilizer of 185.5g calcic and potassium; Secondary crystal concentrates in the Tai-Ace S 150 ammonium alum crystal retort furnace that obtains and returns crystallization enrichment process continuation use after 210 ℃ of dehydrations.
Embodiment 4
5000ml sulfur acid ammonium 1.15wt% waste liquid, earlier through nanofiltration concentrate the trapped fluid of 1000ml sulfur acid ammonium 5.43wt%, see through liquid and return use, trapped fluid is heated to 87 ℃ again, stir and add 1055g Potassium aluminum alum alum flour end, dissolving postcooling to 35 ℃, 1825g exsiccated ammonium alum (potassium) alum crystal is separated out in crystallization; The crystallization concentrated solution that obtains adds ammoniacal liquor adjust pH 6.5 and removes Al
3+After, be heated to 80 ℃, stir adding 75g potassium chloride, ℃ filtration of dissolving postcooling to 50 obtains the thick vitriolate of tartar of 86.4g, and filtrate pressure is cooled to 0 ℃ and gets ammonium-potassium sulfate 60.5g; The ammonium mother liquor returns ammonium salt solution crystallization enrichment process, returns the ammonium salt solution crystallization in exsiccated ammonium alum (potassium) the alum crystal retort furnace after 220 ℃ of dehydrations and concentrates and recycle.
Claims (6)
1. ammonium salt solution concentration method, it is characterized in that, with the enriching agent of dehydration sulfuric acid double salt as ammonium salt solution, concentration process may further comprise the steps: the dehydration sulfuric acid double salt adds rising temperature for dissolving in the ammonium salt solution, crystallisation by cooling is separated out the sulfuric acid double salt crystal of band crystal water, the water of capturing in the solution is concentrated ammonium salt solution, recycles the ammonium salt solution comprehensive utilization after concentrating after the sulfuric acid double salt crystal pyrolysis dehydration that crystallization is separated out; The adding total amount of dehydration sulfuric acid double salt is 0.5～2.0 times of ammonium salt solution crystallization concentration process dehydration quality summation;
Described dehydration sulfuric acid double salt is Tai-Ace S 150 ammonium alum, Tai-Ace S 150 arcanite and the exsiccated ammonium alum of partly or entirely sloughing crystal water and in the potassium aluminium sulfate mixing alum one or more; Ammonium salt in the described solution is meant one or more in ammonium chloride, ammonium nitrate, the ammonium sulfate.
2. method according to claim 1 is characterized in that, described dehydration sulfuric acid double salt rising temperature for dissolving is 50～110 ℃ of stirrings dissolving in 0.2～2.0 hour in ammonium salt solution.
3. method according to claim 1 is characterized in that, described cooling is that nature or pressure are cooled to room temperature.
4. method according to claim 1 is characterized in that, sulfuric acid double salt crystal pyrolysis dehydration is to lose part or all of crystal water in 1～3 hour 80～280 ℃ of pyrolysis, and the dehydration sulfuric acid double salt returns the ammonium salt solution crystallization and concentrates and recycle.
5. method according to claim 1 is characterized in that, described ammonium salt solution is the solution or the waste water of unsaturated ammonium salt-containing under the room temperature.
6. method according to claim 1, it is characterized in that described ammonium salt solution comprehensive utilization is meant that crystallization concentrates the ammonium salt solution that obtains, and further is cooled to-10～10 ℃ of crystallizations and reclaims ammonium salt, or return main technological cycle and use, or spraying drying is produced chemical fertilizer.
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|---|---|---|---|
| CN2009103080007A CN101659422B (en) | 2009-09-29 | 2009-09-29 | Ammonium salt solution concentration method |
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| CN2009103080007A CN101659422B (en) | 2009-09-29 | 2009-09-29 | Ammonium salt solution concentration method |
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| CN101659422A CN101659422A (en) | 2010-03-03 |
| CN101659422B true CN101659422B (en) | 2011-09-14 |
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| CN108530226A (en) * | 2018-05-18 | 2018-09-14 | 高英林 | A kind of highly acid composite fertilizer that phosphorus potassium utilization rate can be made to improve 3 to 5 times |
| CN110104617A (en) * | 2019-04-24 | 2019-08-09 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for alum concentration titanium white waste acid |
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