CN87103546A - From diluted thioamine liquid, reclaim the method for solid ammonium sulfate - Google Patents
From diluted thioamine liquid, reclaim the method for solid ammonium sulfate Download PDFInfo
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- CN87103546A CN87103546A CN87103546.4A CN87103546A CN87103546A CN 87103546 A CN87103546 A CN 87103546A CN 87103546 A CN87103546 A CN 87103546A CN 87103546 A CN87103546 A CN 87103546A
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- ammonium sulfate
- ion
- sulfuric acid
- liquid
- lime
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Abstract
The invention belongs to a kind of from waste liquid the method for reclaim(ed) sulfuric acid ammonium.
Produce a large amount of dilute ammonium sulfate solutions in middle change catalyst production process, because of content is too low, cost recovery is too high, causes environmental pollution and discard.The present invention's lime alkalization, ion-exchange and obtain concentrated ammonium sulfate solution and diluted thioamine liquid is recycled through the regeneration of sulfuric acid resin.This method also can be used for reclaiming the usefulness of weak ammonia and other dilute ammonium salt solutions.
Description
The invention belongs to a kind of from waste liquid the method for reclaim(ed) sulfuric acid ammonium.
Become at present domestic and touch the coal annual production, and the volume of ammonium sulfate (in 100%) that runs off with waste liquid reaches more than 30,000 tons more than 20,000 tons.Past, the sulphur ammonium liquid hold-up of coal production process generation is too low (generally had only 10～15% because middle change is touched, 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 touch coal production usefulness in returning 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, diluted thioamine liquid 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
TwentyBe oxidized to ferric ion Fe
Thirty, and be 7.0～8.0 with ammonia regulator solution pH value, this moment Fe
ThirtyForm 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 passed through 732 (H
+) the type ion exchange resin bed, when effluent liquid is found free ammonia (the ammonia flavor appears in PH noticeable change 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 return and touching the usefulness of preparing burden when coal is produced.Rare ammoniacal liquor stops to enter the exchange bed, drains the solution in the resin bed then.
4, resin regeneration
Industrial sulphuric acid being joined in the sulphuric acid soln 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 sulphuric acid 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 when being concentrated in vacuo to weight then and remaining half left and right sides (this moment is mass crystallization), can stop heating, enters the cooling and stirring crystallizer, carries out the crystallization of chuck cooling and stirring.
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,
The 2-separate pump,
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,
The 12-separator,
13-finished product meter is heavily packed.
Claims (7)
1, a kind of method of receiving solid ammonium sulfate admittedly that reclaims from the dilute sulphuric acid ammonium 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 732[H
+] the type ion 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 7.0～8.0, vacuum concentration, cooling, cooling, stirring again crystallizes 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.
With the said recovery method of claim 1, it is characterized in that 4, it is that said ion exchange resin bed makes the pH value of effluent liquid through washing at 6.0～7.0 o'clock, can return the new rare ammoniacal liquor of absorption.
As the said method of claim 1, it is characterized in that 5, said dihydrate gypsum is removed weak ammonia liquid through precipitation, separation, after the washing oven dry, get gypsum again.
As the said method of claim 1, it is characterized in that 6, the centrifuge mother liquor that crystalline ammonium sulfate obtains can concentrate or do dilute sulphuric acid again and use when centrifugal.
7, as the said method of claim 1, it is characterized in that, containing ferrous ion Fe
TwentyThe dilute sulphuric acid ammonium in first deironing, bubbling air makes ferrous ion Fe
TwentyBe oxidized to ferric ion Fe
Thirty, and the pH value of solution is adjusted to 7.0～8.0 with ammoniacal liquor, make ferric ion Fe
ThirtyForm ferric hydroxide precipitate.
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 true CN87103546A (en) | 1987-11-04 |
| CN1007809B 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600805A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process |
| CN105645514A (en) * | 2016-01-20 | 2016-06-08 | 西北大学 | Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration |
| 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
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600805A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process |
| CN105645514A (en) * | 2016-01-20 | 2016-06-08 | 西北大学 | Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration |
| 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 | The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1007809B (en) | 1990-05-02 |
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