CN87103373A - Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor - Google Patents
Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor Download PDFInfo
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- CN87103373A CN87103373A CN87103373.9A CN87103373A CN87103373A CN 87103373 A CN87103373 A CN 87103373A CN 87103373 A CN87103373 A CN 87103373A CN 87103373 A CN87103373 A CN 87103373A
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- waste liquid
- ammonium sulfate
- sulfuric acid
- iron oxide
- acid pickling
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Abstract
The invention belongs to the recovery method of comprehensive utilization of sulfuric acid pickling waste liquid.This law adopts earlier with the ammoniacal liquor neutralization, makes pH value reach 4.5～5, and the elimination throw out is with deleterious element silicon in the separation waste liquid etc.With bicarbonate of ammonia and wherein ferrous sulfate reaction, generate iron carbonate precipitation and ammonium sulfate again.Iron carbonate generates the product red iron oxide through roasting, and purity reaches more than 99%.Economic worth is higher, and the scope of application is wider, and production cost is lower, except that with the bicarbonate of ammonia, without other raw material.The treated product ammonium sulfate that gets of ammonium sulfate liquor.
Description
The invention belongs to the recovery method of comprehensive utilization of sulfuric acid pickling waste liquid.
Industrial employing sulfuric acid is removed the ferric oxide of steel surface.During pickling, the reaction of the oxide compound of sulfuric acid and iron generates ferrous sulfate.Along with the carrying out of reaction, sulfuric acid concentration reduces, and ferrous sulfate content improves.When acidity drops to finite concentration, must upgrade pickle solution, discharge spent pickle liquor.The sulfuric acid concentration of spent pickle liquor is 2～3%, the about 250g/l of ferrous sulfate content." the metallurgical environmental protection information documents-waste acid treatment technology " that Ministry of Metallurgical Industry Building Research General Institute Institute for Environmental Research edits and publishes, 1983, № 2, to the systematic narration of improvement method of sulfuric acid pickling waste liquid.Wherein, relevant with the present invention recovery method of comprehensive utilization is as follows:
1. in the ammonia and absorption method.Raw materials used ammonia, carbonic acid gas.Product is ammonium sulfate, iron sulphide or ferric oxide.Ferric oxide purity 93% is as steelmaking feed.
2. red iron oxide sulphur ammonium method.Raw materials used ammonia, iron sheet, sulfuric acid, phosphoric acid.Product is ammonium sulfate and red iron oxide.Ferric oxide purity is 96%, and cost is higher, and quality is undesirable.
The purpose of the inventive method is that the quality of red iron oxide is improved, and can be used for making the raw material that coats with lacquer and make magneticsubstance, reduces cost recovery, simplifies technology, reduces initial cost and takes.
The inventive method is earlier with the acid in the ammoniacal liquor neutralisation of sulphuric acid spent pickle liquor, to separate wherein deleterious element silicon etc.When the spent acid pH value reaches 4.5～5, the elimination throw out.Add bicarbonate of ammonia in filtrate, make with ferrous sulfate and react, generate iron carbonate precipitation and ammonium sulfate, temperature of reaction should be not less than 20 ℃, and its reaction equation is:
Leach the iron carbonate precipitation, filter cake is put the stoving oven roasting, and iron carbonate is transformed into the red iron oxide product.Its reaction equation:
With filtrate heating, air-blowing, with till becoming ironic hydroxide after removing ammonia and making the complex compound oxidation of trace iron in the solution and separating out.Centrifuging, filtrate is ammonium sulfate liquor, and its ammonium sulfate content can reach 20～25%.With the ammonium sulfate liquor evaporation concentration, crystallisation by cooling, centrifugal, promptly obtain ammonium sulfate product.
The advantage of the inventive method is: the rate of recovery can reach more than 99%.The product red iron oxide quality that reclaims is good, and purity is more than 99%.Can be used for making the raw material that coats with lacquer and make magneticsubstance, its value ratio wants big more than ten times as steelmaking feed.The ammonium sulfate quality can reach the index of synthetic ammonium sulfate, as agricultural fertilizer.Present method can adopt solid sulphuric acid hydrogen ammonium, the ammonium sulfate concentrations height of generation, and the water yield of evaporation reduces, thereby cost recovery reduces.Because raw material sulphuric acid hydrogen ammonium impurity is few, the ferric sulfate throw out can be removed massive laundering from.Ammonium sulfate product impurity is few, and quality can guarantee.Present method production technique is simpler, and is with short production cycle, all can handle the spent pickle liquor of high density or lower concentration.Initial cost is taken few, can reduce capital cost more than 50% with the comparison of red iron oxide sulphur ammonium method.Present method economic benefit is obvious, as handles the spent pickle liquor that every cubic meter contains 25% ferrous sulfate, and cost is 120 yuan, and income is more than 200 yuan.
The process flow sheet of the inventive method as shown in drawings.Processed sulfuric acid pickling waste liquid, sulfuric acid concentration are below 5%, and ferrous sulfate content is advisable with 250g/l.
Embodiment: spent pickle liquor is neutralized with ammoniacal liquor in neutralizing well.Regulate PH to 4.5～5.Put into reactive tank, when temperature is not less than 20 ℃, slowly add solid ammonium bicarbonate, near reaction end the time, be heated to 40～50 ℃, allow big effusion of carbon dioxide in the solution, with the bicarbonate of ammonia input of remainder, the bicarbonate of ammonia consumption is near the reaction theory value again.Check that no free iron is a reaction end in the solution.
Leach the iron carbonate precipitation, place the pressure filter press filtration, pressure filter can adopt plate-and-frame filter press etc.Filter cake is placed the roasting kiln roasting.Filter cake places 100～150 ℃ of warm area oven dry in the stove earlier, moves to 700～800 ℃ of warm area roastings again.The filter cake box adopts non-scaling steel sheet to make.Product after the roasting is a red iron oxide.The crushing screening of red iron oxide can adopt auger to pulverize and 40 order steel mesh vibration screening.Fineness can reach 320 orders.
The filtrate of elimination iron carbonate post precipitation is heating, air-blowing in heating, air-blowing groove, and solution temperature is not less than 40 ℃.Again with the precipitate centrifugation.Filtrate collection is gone into the ammonium sulfate liquor groove.Ammonium sulfate liquor is evaporation concentration in vaporizer, and temperature is 65 ℃.Insert crystallizer again, with the ammonium sulfate liquor crystallisation by cooling of 45% left and right sides concentration.Crystallization after whizzer separate finished product ammonium sulfate.Centrifugal back liquid is back into the ammonium sulfate liquor groove, again through evaporation, crystallization, recycle.
Claims (6)
1, a kind of method that reclaims comprehensive utilization processing sulfuric acid pickling waste liquid, feature of the present invention is to use in the ammoniacal liquor earlier and the acid in the waste liquid, to separate wherein deleterious element silicon etc., when the spent acid pH value reached 4.5～5, the elimination throw out was when being not less than 20 ℃, in spent pickle liquor, slowly add bicarbonate of ammonia, near reaction end the time, be heated to 40～50 ℃, obtain the ammoniumsulphate soln and the iron carbonate precipitation of high density; Precipitation is leached press filtration, and filter cake is transformed into the red iron oxide product through the roasting iron carbonate; With filtrate heating, air-blowing, centrifuging, to remove trace iron, filtrate is ammonium sulfate liquor, with ammonium sulfate liquor evaporation, concentrated, and crystallisation by cooling, centrifugal, promptly get ammonium sulfate product.
2, the method for processing sulfuric acid pickling waste liquid as claimed in claim 1 is characterized in that the theoretical value of the consumption of bicarbonate of ammonia near contained ferrous sulfate and bicarbonate of ammonia reaction in the waste liquid.
3, the method for processing sulfuric acid pickling waste liquid as claimed in claim 1 is characterized in that the roasting of iron carbonate liquid cake becomes red iron oxide, is earlier filter cake to be placed 100～150 ℃ of warm area oven dry in the stoving oven, moves to 700～800 ℃ of warm area roastings again.
4, the method for processing sulfuric acid pickling waste liquid as claimed in claim 1 is characterized in that the crushing screening of red iron oxide, can adopt auger to pulverize and 40 order steel mesh vibration screening, and fineness can reach 320 orders.
5, the method for processing sulfuric acid pickling waste liquid as claimed in claim 1 is characterized in that the solution temperature in the heating drum air drain is not less than 40 ℃.
6, the method for processing sulfuric acid pickling waste liquid as claimed in claim 1, the vaporization temperature that it is characterized in that the ammonium sulfate liquor evaporation concentration is 65 ℃, crystallisation by cooling liquid concentration is 45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103373 CN1009547B (en) | 1987-05-06 | 1987-05-06 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103373 CN1009547B (en) | 1987-05-06 | 1987-05-06 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103373A true CN87103373A (en) | 1988-11-23 |
| CN1009547B CN1009547B (en) | 1990-09-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87103373 Expired CN1009547B (en) | 1987-05-06 | 1987-05-06 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
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| CN (1) | CN1009547B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036775C (en) * | 1994-03-16 | 1997-12-24 | 南京化学工业(集团)公司研究院 | Method for production of high-content ferric oxide red colorant from iron-contained industrial burned dregs |
| CN100361905C (en) * | 2006-04-28 | 2008-01-16 | 常州市裕和金属材料有限公司 | Method for treating waste acid liquor |
| CN101177284B (en) * | 2007-11-02 | 2010-06-02 | 北京化工大学 | Method for reclaiming sulfuric ammonium and ferric oxide from sulfuric acid pickling waste fluid |
| CN101367085B (en) * | 2008-05-20 | 2010-11-10 | 马鞍山钢铁股份有限公司 | Acid washing iron red desilication filter cake treating device and treating method |
| CN103723776A (en) * | 2014-01-01 | 2014-04-16 | 郭秋丰 | Joint production method of iron oxide and ammonium sulfate |
| CN103818968A (en) * | 2014-01-07 | 2014-05-28 | 中国神华能源股份有限公司 | Iron oxide red and preparation method thereof |
| CN103818969A (en) * | 2014-01-07 | 2014-05-28 | 中国神华能源股份有限公司 | Iron oxide red and preparation method thereof |
| CN104045115A (en) * | 2013-10-30 | 2014-09-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of iron oxide used for high-grade soft-magnetic materials |
| CN105217694A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing red iron oxide and ammonium chloride |
| CN107694747A (en) * | 2017-09-29 | 2018-02-16 | 铜陵有色金属集团股份有限公司冬瓜山铜矿 | The method of comprehensive utilization of spent acid in gas washing in SA production |
| CN107841621A (en) * | 2016-09-20 | 2018-03-27 | 张家港格林台科环保设备有限公司 | A kind of method that high-grad iron ore deposit is produced using pickling iron cement |
| WO2021017940A1 (en) * | 2019-07-29 | 2021-02-04 | 中冶南方工程技术有限公司 | Method for hazard-free treatment of sludge from spent solution of mixed acids after acid washing of stainless steel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294087C (en) * | 2003-10-08 | 2007-01-10 | 山西焦化股份有限公司 | Method for treating waste acid from refining benzene for coking plant |
-
1987
- 1987-05-06 CN CN 87103373 patent/CN1009547B/en not_active Expired
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036775C (en) * | 1994-03-16 | 1997-12-24 | 南京化学工业(集团)公司研究院 | Method for production of high-content ferric oxide red colorant from iron-contained industrial burned dregs |
| CN100361905C (en) * | 2006-04-28 | 2008-01-16 | 常州市裕和金属材料有限公司 | Method for treating waste acid liquor |
| CN101177284B (en) * | 2007-11-02 | 2010-06-02 | 北京化工大学 | Method for reclaiming sulfuric ammonium and ferric oxide from sulfuric acid pickling waste fluid |
| CN101367085B (en) * | 2008-05-20 | 2010-11-10 | 马鞍山钢铁股份有限公司 | Acid washing iron red desilication filter cake treating device and treating method |
| CN104045115A (en) * | 2013-10-30 | 2014-09-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of iron oxide used for high-grade soft-magnetic materials |
| CN104045115B (en) * | 2013-10-30 | 2016-04-27 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of the ferric oxide for high-grade soft magnetic materials |
| CN103723776B (en) * | 2014-01-01 | 2015-02-04 | 柳纪申 | Joint production method of iron oxide and ammonium sulfate |
| CN103723776A (en) * | 2014-01-01 | 2014-04-16 | 郭秋丰 | Joint production method of iron oxide and ammonium sulfate |
| CN103818969A (en) * | 2014-01-07 | 2014-05-28 | 中国神华能源股份有限公司 | Iron oxide red and preparation method thereof |
| CN103818968A (en) * | 2014-01-07 | 2014-05-28 | 中国神华能源股份有限公司 | Iron oxide red and preparation method thereof |
| CN103818969B (en) * | 2014-01-07 | 2016-02-10 | 中国神华能源股份有限公司 | Red iron oxide and preparation method thereof |
| CN103818968B (en) * | 2014-01-07 | 2016-08-24 | 中国神华能源股份有限公司 | The preparation method of iron oxide red |
| CN105217694A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing red iron oxide and ammonium chloride |
| CN107841621A (en) * | 2016-09-20 | 2018-03-27 | 张家港格林台科环保设备有限公司 | A kind of method that high-grad iron ore deposit is produced using pickling iron cement |
| CN107694747A (en) * | 2017-09-29 | 2018-02-16 | 铜陵有色金属集团股份有限公司冬瓜山铜矿 | The method of comprehensive utilization of spent acid in gas washing in SA production |
| WO2021017940A1 (en) * | 2019-07-29 | 2021-02-04 | 中冶南方工程技术有限公司 | Method for hazard-free treatment of sludge from spent solution of mixed acids after acid washing of stainless steel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1009547B (en) | 1990-09-12 |
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