CN1007809B - Method of recovering solid ammonium sulfate from dilute ammonium sulfate solution - Google Patents
Method of recovering solid ammonium sulfate from dilute ammonium sulfate solutionInfo
- Publication number
- CN1007809B CN1007809B CN 87103546 CN87103546A CN1007809B CN 1007809 B CN1007809 B CN 1007809B CN 87103546 CN87103546 CN 87103546 CN 87103546 A CN87103546 A CN 87103546A CN 1007809 B CN1007809 B CN 1007809B
- Authority
- CN
- China
- Prior art keywords
- ammonium sulfate
- sulfuric acid
- lime
- dilute
- solution
- 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.)
- Expired
Links
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The present invention belongs to a method for recovering ammonium sulfate from waste liquid. A large quantity of diluted ammonium sulphate solution generated in the production of medium temperature conversion catalysts is discarded to cause environmental pollution because of the disadvantages of low content and high recovery cost. The present invention obtains concentrated ammonium sulphate solution through lime alkalization, ion exchange and resin regeneration by sulphuric acid, so that diluted ammonium sulfate solution is recycled. The method can also be used for recovering diluted ammonia water and other diluted ammonium salt solutions.
Description
The invention belongs to a kind of from waste liquid the method for reclaim(ed) sulfuric acid ammonium.
Become the catalyst annual production at present domestic more than 20,000 tons, and the volume of ammonium sulfate (in 100%) that runs off with waste liquid reaches more than 30,000 tons.Past (generally has only 10～15% because the ammonium sulfate liquid hold-up that middle change catalyst production process produces is too low, be low to moderate 0.5～2% and washing lotion has) as producing solid ammonium sulfate with direct method of enrichment, then too big because of consumption of coal, cost surpasses value of the product and can't recycle, flow into rivers in vain, cause environmental pollution on the contrary.
Recovery method of the present invention can make ammonium sulfate generate saturated solution, and reduces consumption of coal greatly, can make waste water return the middle catalyst production usefulness that becomes simultaneously, has eliminated waste liquid fully, has both eliminated source of pollution, turns waste into wealth again.
Recovery method step of the present invention is as follows:
1, dilute ammonium sulfate solution deironing
If waste liquid contains irony, then at first with ammonium sulfate liquid (comprising that mother liquor and washing lotion mix), bubbling air carries out oxide treatment, makes ferrous ion Fe remaining in the solution
+ 2Be oxidized to ferric ion Fe
+ 3, and be 7.0～8.0 with ammonia regulator solution pH value, this moment Fe
+ 3Form Fe(OH)
3And precipitating is come out, the solution after handling through deironing with lime reaction after, the dihydrate gypsum color of generation is whiter.
2, lime treatment
After deironing is handled, add milk of lime and stir (available replacing carbide slag with lime breast, but the gypsum by product that obtains of carbide slag can only be used for manufacture of cement, and lime reaction draws pays cultivation that the product gypsum can be used for other industry and mushroom etc.), make to generate dihydrate gypsum and weak ammonia, dihydrate gypsum separates through post precipitation centrifugal (or filtration, suction strainer), through washing, oven dry can be worked as and be paid the product sale again, the cost of general recoverable lime also shows a small surplus.
3, ion-exchange
Weak ammonia liquid is exchange resin bed by polystyrene or acrylic acid cation, (PH noticeable change when effluent liquid is found free ammonia, the ammonia flavor appears simultaneously), illustrate that promptly ion exchange bed is saturated by the ammonia exchange, can return when water usefulness through the effusive liquid of ion exchange bed, be used to prepare ferrous sulfate, promptly returning prepares burden when catalyst is produced uses.Rare ammoniacal liquor stops to enter the exchange bed, drains the solution in the resin bed then.
4, resin regeneration
The industrial vitriol oil being joined in the dilute ammonium sulfate solution under stirring dilute, is 30～40% to content, also available industrial waste sulfuric acid, for example sulfur waste acid of 70% content after the Trichlorphon production process.Through the saturated resin bed of ammonia, when the pH value of effluent liquid (being the ammonium sulfate saturated solution) reaches 1.0, promptly should stop to add sulfuric acid liquid, and drain the ammoniumsulphate soln in the resin bed above entering then.The washed resin bed is till effluent liquid PH=6.0～7.0 then, and resin bed has obtained regeneration, can return again to have absorbed new ammoniacal liquor.
5, the ammonium sulfate finished product is made
Is 8.0 through the effusive ammonium sulfate saturated solution of resin bed with the liquefied ammonia pH value that neutralizes, and is concentrated to weight then when remaining half left and right sides (this moment is mass crystallization), can stop heating, enters crystallizer, carries out crystallization.
Crystallisate is through centrifugation, and oven dry can be packaged as the ammonium sulfate finished product and sell.
Centrifuge mother liquor can return concentrated, uses when also can be used for dilute sulphuric acid.
Process flow sheet of the present invention is seen accompanying drawing.101 is the iron-free dilute ammonium sulfate solution among the figure, and 102 is milk of lime (or carbide slag), and 103 for paying the product dihydrate gypsum, and 104 is industrial sulphuric acid or industrial waste sulfuric acid, and 105 is water or dilute ammonium sulfate solution.
Being labeled as of each device:
1-dilute sulphuric acid ammonium and milk of lime reactor,
2-solid-liquid separator,
The rare ammonium liquid of 3-Receiving bin,
The 4-pump,
The rare ammonium liquid of 5-potentiostat,
The 6-sulfuric acid dilution device,
The 7-acid proof pump,
8-sulfuric acid potentiostat,
The 9-ion-exchanger,
The 10-thickener,
The 11-crystallizer,
12-solid-liquid separator,
13-finished product meter is heavily packed.
Claims (5)
1, a kind of from dilute ammonium sulfate solution the method for reclaim(ed) sulfuric acid ammonium, it is characterized in that,
A) lime treatment: in dilute ammonium sulfate solution, add lime and stir generation dihydrate gypsum and weak ammonia liquid,
B) ion-exchange: weak ammonia liquid is passed through polystyrene or acrylic acid type cation exchange resin bed; This ion exchange resin bed is absorbed reach ammonia behind ammoniacal liquor saturated,
C) form solid ammonium sulfate: sulfuric acid is added dilute ammonium sulfate solution, making sulfuric acid content is 30～40%, pass through the saturated ion exchange resin bed of said ammonia then, obtain the ammonium sulfate saturated solution, reaching pH value with the liquefied ammonia neutralization again is 8.0, again through concentrating, lower the temperature, cool off, stirring, crystallize into solid ammonium sulfate at last.
As the said recovery method of claim 1, it is characterized in that 2, said lime is milk of lime or carbide slag.
3,, it is characterized in that said sulfuric acid is industrial sulphuric acid or industrial waste sulfuric acid as the said recovery method of claim 1.
As the said recovery method of claim 1, it is characterized in that 4, said dihydrate gypsum is removed weak ammonia liquid through precipitation, separation, after the washing oven dry, obtain gypsum again.
As the said recovery method of claim 1, it is characterized in that 5, the centrifuge mother liquor that crystalline ammonium sulfate obtains can concentrate or do dilute sulphuric acid again and use when centrifugal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103546 CN1007809B (en) | 1987-05-18 | 1987-05-18 | Method of recovering solid ammonium sulfate from dilute ammonium sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103546 CN1007809B (en) | 1987-05-18 | 1987-05-18 | Method of recovering solid ammonium sulfate from dilute ammonium sulfate solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103546A CN87103546A (en) | 1987-11-04 |
| CN1007809B true CN1007809B (en) | 1990-05-02 |
Family
ID=4814483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87103546 Expired CN1007809B (en) | 1987-05-18 | 1987-05-18 | Method of recovering solid ammonium sulfate from dilute ammonium sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007809B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600805B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A kind of method that ammonium sulfate is isolated and purified in the regenerative process by-product solution from fume desulfurizing agent |
| CN105645514B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A separation and purification method of ammonium sulfate and sodium sulfate mixed solution in the regeneration process of flue gas desulfurizer |
| CN109289938A (en) * | 2018-10-30 | 2019-02-01 | 扬州金珠树脂有限公司 | The separation of sulfuric acid and the method for covering sour reuse in a kind of ion exchange resin hydrolyzate |
-
1987
- 1987-05-18 CN CN 87103546 patent/CN1007809B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87103546A (en) | 1987-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3569720A1 (en) | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor | |
| CN107117652B (en) | A kind of method for obtaining ammonium metavanadate from alkaline vanadium-containing solution | |
| CN85101989A (en) | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 | |
| CN1966400A (en) | Method for treating waste acid produced from titanium dioxide production using vitriol method | |
| CN112499813A (en) | Production method for full resource recycling of waste water in titanium dioxide production by sulfuric acid process | |
| CN101774557A (en) | Method for producing phosphoric acid with titanium white waste | |
| CN1007809B (en) | Method of recovering solid ammonium sulfate from dilute ammonium sulfate solution | |
| FR2357479A1 (en) | PROCESS FOR THE PRODUCTION OF SULFURIC ACID FROM RESIDUAL ACIDS AND IRON SULPHATE | |
| CN1067269A (en) | With delafossite wet method direct production copper sulfate process | |
| CN108128788A (en) | A kind of method that sodium sulphate is recycled in the waste water from desulphurization denitration | |
| CN111661828A (en) | Preparation method of high-purity reagent nitric acid | |
| CN208802942U (en) | A kind of high ammonia nitrogen sulfuric acid copper waste water environmental protection recyclable device of zero-emission | |
| CN108640162B (en) | Alkali circulation iron-containing solid waste iron oxide pigment production equipment system | |
| CN1044222C (en) | Comprehensive utilization method of chromium-containing sodium sulfate | |
| CN215516666U (en) | A spent acid integrated processing device for titanium white powder production | |
| CN87102046A (en) | Method with producing manganous sulphate solution from manganese dioxide ore | |
| CN109809582A (en) | A kind of potassium sulfate Sewage treatment utilizes method | |
| CN1035093A (en) | A kind of technology for removal of magnesium from phosphorous ore | |
| CN85105036A (en) | Preparation process of nitrogen-zinc compound fertilizer | |
| CN103482653A (en) | Method utilizing flue gas sulfuric acid to produce ammonium sulfate | |
| CN1050367A (en) | A kind of method of producing single nickel salt | |
| CN1014698B (en) | Method for producing ammonium molybdate and ammonium nickel sulfate from molybdenum-nickel ore | |
| CN1025562C (en) | Preparation process of hydroxyalkanesulfonic acid for electroplating solution | |
| CN104628033A (en) | Method for preparing metavanadate | |
| CN118515309B (en) | Recycling method of titanium phosphate product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |