CN103482653B - A kind of method of flue gas gas washing in SA production ammonium sulfate - Google Patents
A kind of method of flue gas gas washing in SA production ammonium sulfate Download PDFInfo
- Publication number
- CN103482653B CN103482653B CN201310446765.3A CN201310446765A CN103482653B CN 103482653 B CN103482653 B CN 103482653B CN 201310446765 A CN201310446765 A CN 201310446765A CN 103482653 B CN103482653 B CN 103482653B
- Authority
- CN
- China
- Prior art keywords
- ammonium sulfate
- ammonia
- flue gas
- sulfuric acid
- until
- 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.)
- Active
Links
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention provides a kind of method of flue gas gas washing in SA production ammonium sulfate.Said method comprising the steps of: (1) prepares the ammonia soln that pH value is 11 ~ 13; (2) in described ammonia soln, flue gas sulfuric acid is added until the pH value of gained mixed solution is 3 ~ 5; (3) ammonia is passed into until the pH value of gained mixed solution is 11 ~ 13; (4) repeatedly carry out step (2) and (3), until ammonia sulfate crystal is separated out in the ammoniumsulphate soln supersaturation that reaction generates, filter and obtain ammonium sulfate.Method Appropriate application industrial smoke sulfuric acid of the present invention, and the ammonium sulfate obtained can as the raw material of hydrometallurgy, there is simple to operate, sulfuric acid and ammonia utilization ratio high, cost-saving and promote the advantage that environmental protection and waste resource fully utilize.
Description
Technical field
The present invention relates to chemical technology field, more particularly, relate to a kind of method utilizing industrial smoke sulfuric acid to generate ammonium sulfate.
Background technology
Ammonium salt is important leaching agent in hydrometallurgy and precipitation agent.Prepare ammonium sulfate at present and mainly contain following two kinds of methods.
A kind of method is publication number for the scrubbing CO_2 from stack gas disclosed in the Chinese patent of CN1401414A and the method for obtained ammonium sulfate.The method is scrubbing CO_2 from stack gas, sulfurous gas passes through ammonium sulfite solution, sulfurous gas in ammonium sulphite and stack gas and water react and generate bisulfite ammonium solution, again to ammonification in bisulfite ammonium solution, reaction generates ammonium sulfite solution, in oxygen-containing gas, use electron beam irradiation ammonium sulphite again, make it to generate ammonium sulfate.This method is unstable at preparation process sulfite ammonium, and oxidation needs to carry out in the solution, and the ammoniumsulphate soln concentration of generation is low, needs to concentrate further just can obtain ammonium sulfate solids.
Another kind method is publication number is the method preparing large-particle ammonium sulfate disclosed in the Chinese patent of CN1051711C.The method is that the by product ammoniumsulphate soln preparing lactan is input to crystallizer condensing crystal, and by tripping device reclaim(ed) sulfuric acid ammonium crystal from the slurry containing crystalline sulfuric acid ammonium.This method is just further processed ready-made ammonium sulfate, obtains the ammonia sulfate crystal of more good quality, does not relate to production ammonium sulfate.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to solve in above-mentioned prior art the one or more problems existed.
The invention provides a kind of method of flue gas gas washing in SA production ammonium sulfate.Said method comprising the steps of: (1) prepares the ammonia soln that pH value is 11 ~ 13; (2) in described ammonia soln, flue gas sulfuric acid is added until the pH value of gained mixed solution is 3 ~ 5; (3) ammonia is passed into until the pH value of gained mixed solution is 11 ~ 13; (4) repeatedly carry out step (2) and (3), until ammonia sulfate crystal is separated out in the ammoniumsulphate soln supersaturation that reaction generates, filter and obtain ammonium sulfate.
According to an embodiment of the method for flue gas gas washing in SA production ammonium sulfate of the present invention, the filtrate that in described step (4), filtration obtains returns in step (1) and recycles.
According to an embodiment of the method for flue gas gas washing in SA production ammonium sulfate of the present invention, the mass percentage concentration of described flue gas sulfuric acid is 93 ~ 98%.
Compared with prior art, beneficial effect of the present invention comprises: Appropriate application industry byproduct flue gas sulfuric acid, and the ammonium sulfate obtained can as the raw material of hydrometallurgy, there is simple to operate, sulfuric acid and ammonia utilization ratio high, cost-saving and promote the advantage that environmental protection and waste resource fully utilize.
Embodiment
Hereinafter, the method according to flue gas gas washing in SA production ammonium sulfate of the present invention will be described in detail in conjunction with exemplary embodiment.
Obtain sulphur trioxide by catalyst oxidation after the sulphur dioxide enrichment that iron and steel enterprise or coal chemical industry enterprises desulfurization produce, then after dust filtration equipment filters, absorb the sulfuric acid obtained with water be called flue gas sulfuric acid, the mass percentage concentration of flue gas sulfuric acid is 93 ~ 98%.As industry byproduct, its output is large, but flue gas sulfuric acid contains more impurity, and quality does not have industrial sulphuric acid good, so there is no be effectively utilized, and directly discharges environmental disruption effect large.
Method of the present invention with described flue gas sulfuric acid for ammonium sulfate prepared by raw material.Comprise the following steps by the method for flue gas gas washing in SA production ammonium sulfate according to an exemplary embodiment of the present invention:
(1) ammonia soln that pH value is 11 ~ 13 is prepared.Such as, ammonia can be passed into or pass into ammonia in water in the ammonia soln of mass percentage concentration below 20%.
(2) in ammonia soln, flue gas sulfuric acid is added until the pH value of gained mixed solution is 3 ~ 5.
(3) ammonia is passed into until the pH value of gained mixed solution is 11 ~ 13.
(4) repeatedly carry out step (2) and (3), until ammonia sulfate crystal is separated out in the ammoniumsulphate soln supersaturation that reaction generates, filter and obtain ammonium sulfate.Filter the ammonium sulfate that obtains and obtain ammonium sulfate solids after drying, and filter the filtrate obtained and return in step (1) and recycle.
It should be noted that, method of the present invention need be carried out and Controlling Technology parameter in strict accordance with above processing step, could obtain ammonium sulfate.Namely the pH value of above steps solution exceedes the upper limit or the lower limit of respective range value, and method of the present invention just can not be implemented; Need in addition repeatedly to carry out step (2) and (3), ammonia sulfate crystal is separated out in the ammoniumsulphate soln supersaturation that reaction just can be made to generate, and only carries out a step (2) and (3) do not reach corresponding technique effect; In addition, the mass percentage concentration of the industry byproduct flue gas sulfuric acid adopted controls to be 93 ~ 98%, if the mass percentage concentration of flue gas sulfuric acid is too low, is unfavorable for that reaction generates ammonium sulfate.
In order to understand above-mentioned exemplary embodiment of the present invention better, below in conjunction with concrete example, it is further described.It should be noted that, in the examples below, unless otherwise indicated, otherwise the reagent used is analytical reagent, the water that the water of use is distilled water or deionized water or suitable purity.
Example 1
Get 1L water in 5L beaker, pass into for some time ammonia until solution ph is between 12 ~ 13, stop logical ammonia; Stirring adds flue gas sulfuric acid until pH value of solution is between 3 ~ 4, logical ammonia is until solution ph is 12 ~ 13 again, flue gas sulfuric acid is added until pH is between 3 ~ 4 after stopping logical ammonia, so repeatedly carry out adding flue gas sulfuric acid and passing into the operation of ammonia until produce a large amount of white ammonium sulfate solids, solid and the general 1:1 of supernatant liquid volume ratio after sedimentation, filtration obtains white ammonium sulfate solids and upper liquid, mend in upper liquid and add water to liquor capacity 1L in beaker, continue above-mentioned intersection and add flue gas sulfuric acid and the operation passing into ammonia, until separate out a large amount of white ammonium sulfate solids.Repeatable operation like this, until operation stops, last is taken turns, and remaining filtrate is air-dry directly obtains ammonium sulfate solids afterwards.
Example 2
Get 1L water in 5L beaker, pass into for some time ammonia until solution ph is between 11 ~ 12, stop logical ammonia; Stirring adds flue gas sulfuric acid until pH value of solution is between 4 ~ 5, logical ammonia is until solution ph is 11 ~ 12 again, flue gas sulfuric acid is added until pH is between 4 ~ 5 after stopping logical ammonia, so repeatedly carry out adding flue gas sulfuric acid and passing into the operation of ammonia until produce a large amount of white ammonium sulfate solids, solid and the general 1:1 of supernatant liquid volume ratio after sedimentation, filtration obtains white ammonium sulfate solids and upper liquid, mend in upper liquid and add water to liquor capacity 1L in beaker, continue above-mentioned intersection and add flue gas sulfuric acid and the operation passing into ammonia, until separate out a large amount of white ammonium sulfate solids.Repeatable operation like this, until operation stops, last is taken turns, and remaining filtrate is air-dry directly obtains ammonium sulfate solids afterwards.
Example 3
Measure 1L mass percentage concentration be the ammoniacal liquor of 20% in 5L beaker, pass into for some time ammonia until solution ph is between 12 ~ 13, stop logical ammonia, stirring adds flue gas sulfuric acid until pH value of solution is between 4 ~ 5, logical ammonia is until solution ph is 12 ~ 13 again, flue gas sulfuric acid is added until pH is between 4 ~ 5 after stopping logical ammonia, so repeatedly carry out adding flue gas sulfuric acid and passing into the operation of ammonia until produce a large amount of white ammonium sulfate solids, solid and the general 1:1 of supernatant liquid volume ratio after sedimentation, filtration obtains white ammonium sulfate solids and upper liquid, add in upper liquid mass percentage concentration be 20% ammoniacal liquor to the liquor capacity in beaker be 1L, continue above-mentioned intersection and add flue gas sulfuric acid and the operation passing into ammonia, until separate out a large amount of white ammonium sulfate solids.Repeatable operation like this, until operation stops, last is taken turns, and remaining filtrate is air-dry directly obtains ammonium sulfate solids afterwards.
In sum, method of the present invention utilizes flue gas sulfuric acid to prepare ammonium sulfate, solves the recycling problem of flue gas sulfuric acid; be conducive to environment protection; and the ammonium sulfate obtained as the raw material of hydrometallurgy, for the iron and steel enterprise of hydrometallurgy directly provides ammonium salt, can reduce transportation cost.There is simple to operate, sulfuric acid and ammonia utilization ratio high, cost-saving and promote the advantage that environmental protection and waste resource fully utilize.
Although above by describing the present invention in conjunction with exemplary embodiment, it will be apparent to those skilled in the art that when not departing from the spirit and scope that claim limits, various amendment and change can be carried out to exemplary embodiment of the present invention.
Claims (2)
1. by a method for flue gas gas washing in SA production ammonium sulfate, it is characterized in that, said method comprising the steps of:
(1) ammonia soln that pH value is 11 ~ 13 is prepared;
(2) in described ammonia soln, flue gas sulfuric acid is added until the pH value of gained mixed solution is 3 ~ 5;
(3) ammonia is passed into until the pH value of gained mixed solution is 11 ~ 13;
(4) repeatedly carry out step (2) and (3), until ammonia sulfate crystal is separated out in the ammoniumsulphate soln supersaturation that reaction generates, filter and obtain ammonium sulfate;
The mass percentage concentration of described flue gas sulfuric acid is 93 ~ 98%.
2. the method for flue gas gas washing in SA production ammonium sulfate according to claim 1, is characterized in that, the filtrate that filtration in described step (4) obtains is returned in step (1) and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310446765.3A CN103482653B (en) | 2013-09-27 | 2013-09-27 | A kind of method of flue gas gas washing in SA production ammonium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310446765.3A CN103482653B (en) | 2013-09-27 | 2013-09-27 | A kind of method of flue gas gas washing in SA production ammonium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103482653A CN103482653A (en) | 2014-01-01 |
| CN103482653B true CN103482653B (en) | 2015-10-14 |
Family
ID=49823325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310446765.3A Active CN103482653B (en) | 2013-09-27 | 2013-09-27 | A kind of method of flue gas gas washing in SA production ammonium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103482653B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800648B (en) * | 2016-03-07 | 2018-02-02 | 攀钢集团攀枝花钢钒有限公司 | The Application way for the ammonium sulfate that flue gas during smelting is produced |
| CN112811440A (en) * | 2021-03-03 | 2021-05-18 | 西安热工研究院有限公司 | System and method for preparing ammonium sulfate by using boiler sulfur-containing flue gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1267692A (en) * | 1968-04-16 | 1972-03-22 | Bayer Ag | Process for the recovery of ammonia |
| CN101503203A (en) * | 2009-03-17 | 2009-08-12 | 杨绍泉 | Method for decomposing ammonia sulfate and method for reclaiming sulfuric acid from waste acid and acid wastewater |
| CN102899492A (en) * | 2012-10-24 | 2013-01-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for utilizing flue gas sulfuric acid |
| CN103159232A (en) * | 2011-12-13 | 2013-06-19 | 赵建鹏 | Method for synthesizing ammonium sulfate by using recovered ammonia water from chemical fertilizer plant |
| CN103318918A (en) * | 2013-05-14 | 2013-09-25 | 武汉百富环保工程有限公司 | Method for purification and recovery of ammonia gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3431207B2 (en) * | 1993-04-16 | 2003-07-28 | 住金エア・ウォーター・ケミカル株式会社 | Manufacturing method of granular ammonium sulfate |
-
2013
- 2013-09-27 CN CN201310446765.3A patent/CN103482653B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1267692A (en) * | 1968-04-16 | 1972-03-22 | Bayer Ag | Process for the recovery of ammonia |
| CN101503203A (en) * | 2009-03-17 | 2009-08-12 | 杨绍泉 | Method for decomposing ammonia sulfate and method for reclaiming sulfuric acid from waste acid and acid wastewater |
| CN103159232A (en) * | 2011-12-13 | 2013-06-19 | 赵建鹏 | Method for synthesizing ammonium sulfate by using recovered ammonia water from chemical fertilizer plant |
| CN102899492A (en) * | 2012-10-24 | 2013-01-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for utilizing flue gas sulfuric acid |
| CN103318918A (en) * | 2013-05-14 | 2013-09-25 | 武汉百富环保工程有限公司 | Method for purification and recovery of ammonia gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103482653A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104096707B (en) | Semi-dry desulphurization ash resource utilization method | |
| CN103849765B (en) | A kind of precipitate and separate and the method reclaiming vanadium and chromium in vanadium chromium solution | |
| CN106115742B (en) | A kind of technique of two step method Cycle-decomposition trans-utilization ardealite | |
| CN103482653B (en) | A kind of method of flue gas gas washing in SA production ammonium sulfate | |
| CN103304090B (en) | Device and method for recycling waste sulfate in sulfate acid-making system | |
| CN101474530A (en) | Wet-type ammonia process three-circulation desulphurization technique suitable for sintered flue gas | |
| CN103626222B (en) | A kind of preparation method of micron order tin dioxide powder | |
| CN101531384A (en) | Technique for preparing electronic grade magnesium hydrate and ammonium sulphate by cycle serum featuring in flue gas desulfurization by method of magnesium oxidization | |
| CN102849795B (en) | Preparation of high-purity vanadium pentoxide | |
| CN105013317A (en) | Process flow for recovering high-purity magnesium sulfite by magnesium oxide flue gas desulphurization | |
| CN102976359A (en) | Method for producing ammonium sulfate by removing sulfur through ammonia method | |
| CN104761295A (en) | Production method of calcium superphosphate | |
| CN205461742U (en) | Novel dual alkali scrubbing FGD process system | |
| CN103691283A (en) | Method for fixing carbon dioxide in industrial smoke | |
| CN101898770B (en) | Method for recycling sodium hydroxide | |
| US20170306443A1 (en) | Novel Method for Extracting Ultra High Purity Alumina from Wastewater | |
| CN103553078A (en) | Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization | |
| CN109721080A (en) | A kind of production technology of desulfurization sodium sulfite | |
| CN106430713A (en) | Wet desulphurization wastewater zero-discharge treatment device | |
| CN103373734B (en) | Method for preparing high-quality potassium rhodanide by using coke oven gas waste liquor with sulfur and cyanogen removed | |
| CN107934993B (en) | A method of anhydrous sodium sulfate is prepared using saltcake containing chromium | |
| CN109455761A (en) | A method of removing vanadium from molybdate solution | |
| Li et al. | Calcium sulfite oxidation and crystal growth in the process of calcium carbide residue to produce gypsum | |
| CN104645815B (en) | A kind of preparation method of manganese sulfate | |
| CN103159232A (en) | Method for synthesizing ammonium sulfate by using recovered ammonia water from chemical fertilizer plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |