CN101177284B - Method for reclaiming sulfuric ammonium and ferric oxide from sulfuric acid pickling waste fluid - Google Patents
Method for reclaiming sulfuric ammonium and ferric oxide from sulfuric acid pickling waste fluid Download PDFInfo
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- CN101177284B CN101177284B CN2007101767415A CN200710176741A CN101177284B CN 101177284 B CN101177284 B CN 101177284B CN 2007101767415 A CN2007101767415 A CN 2007101767415A CN 200710176741 A CN200710176741 A CN 200710176741A CN 101177284 B CN101177284 B CN 101177284B
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Abstract
The invention relates to a reclaiming method of ammonium sulfate and iron oxide from sulfuric acid pickling liquor, belonging to the environmental protection field. The common ammonium neutralization method has the disadvantages that the generated sediment and ammonium sulfate solution are difficult to separate; the ammonium sulfate contains too much impurity with poor quality and the ammonia recovery rate is low. The method is as follow: the pickling liquor is filtered with a prefilter for removing solid grain impurity, and then enters into a neutralization reactor to perform neutralization reaction with ammonia liquor and ammonia gas, and when the reaction PH value reaches between 8 to 11.5, sediment is generated; organic flocculating agent is added in the neutralization reaction stage and then the pickling liquor enters into sedimentation filter to filter and separate; the filtered fluid is heated and then is filtered further for filtration and impurity removal; filter residue is discharged into the sedimentation filter and the secondary filter liquor is vaporized and crystallized in an evaporating crystallizer and ammonium sulfate with white color is acquired; the filter cake is spray-washed in a spray washing device with ammonia liquor and the bioleached ammonia liquor from spray washing is used as ammonia liquor feeding material of the neutralization reactor; after spray washing, the filter cake is heated and dried with a dryer and the distilled ammonia gas returns to the neutralization reactor. The invention has the advantages that the sediment is easily separated from the ammonium sulfate solution and the produced ammonium sulfate has little impurity with high ammonium recovery rate.
Description
Technical field:
The present invention relates to a kind of Pollution abatement and resource recycling technology of industrial sulphuric acid spent pickle liquor, belong to the environment protection category.
Background technology:
The iron and steel processing industry will adopt pickling to remove the ferric oxide on surface before multiple steel treatment process such as phosphatization, welding.The metallic iron reaction on sulfuric acid and ferric oxide and surface mainly generates ferrous sulfate during pickling.Along with the carrying out of reaction, ferrous sulfate content raises, and the acidity of pickle solution reduces.When the pickle solution sulfuric acid concentration is reduced to 2-3%, must upgrade pickle solution, the ferrous sulfate weight percentage of this moment is about 20%.The spent pickle liquor of discharging must obtain administering, and common improvement method has:
1, legal in the lime.Add lime powder in spent pickle liquor, generate gypsum and ferric oxide mixed serum, filter the back mud cake and do the sanitary landfill processing, filtrate is returned the pickling tub reuse.This technology still produces a large amount of solid waste, and iron resources wherein is wasted.
2, with the spent pickle liquor be the raw material production water treatment coagulant.Owing to limited by product consumption scale, and may contain reason such as harmful heavy metal ion in the spent pickle liquor, this method is limited to, and can not solve waste water on a large scale.
3, in the ammonia and absorption method.Raw materials used is ammonia, carbonic acid gas, and product is ammonium sulfate, iron sulphide or ferric oxide.Ammonium sulfate can be used as chemical fertilizer, and ferric oxide can be used as iron-smelting raw material.This class methods application prospect is better, but owing to had iron oxide precipitation and the ammoniumsulphate soln separation difficulty that generates in the technology, and because the ammonium sulfate purity that obtains is lower, reasons such as inferior quality, such technology still need continue to improve. in the past
Summary of the invention
The objective of the invention is to use ammonia neutralization precipitation principle, with deleterious sulfuric acid pickling waste liquid recycling.The principle of chemical reaction is as follows:
The fine particle precipitation solid-liquid separation that above-mentioned reaction forms is difficulty very, can strengthen the separating effect that precipitates with ammoniumsulphate soln by means of the present invention, improves the quality quality of ammonium sulfate product, and improves the utilising efficiency of ammonia.For achieving the above object, embodiment of the present invention are as follows:
At first spent pickle liquor filter to be removed solid particle polluter by primary filter, and waste liquid enters neutralization reactor then, in neutralization reactor with ammoniacal liquor and ammonia generation neutralization reaction, when pH value in reaction 8～11.5 the time, form precipitation more fully.Carrying out in neutralization reaction that the stage adds with respect to the waste liquid weight percent is 0.005%～0.05% organic floculants such as polyacrylamide, sodium polyacrylate or polyethylene benzene sulfonic acid sodium salt, and the input deposition filter carries out filtering separation.The filtrate of deposition filter need be heated to 60～105 ℃, and keeps constant temperature 5～60 minutes; After the filtrate heating, through the filtering and impurity removing once more of filter again; Filter residue is discharged to deposition filter, and the secondary filtrate is evaporated in evaporative crystallizer, crystallization, obtains the pure white ammonium sulfate of color and luster, can be used as the chemical fertilizer commodity selling; Exhaust steam can be made other purposes as the low-quality thermal source.The filter cake of deposition filter is used ammoniacal liquor drip washing in leaching device, the drop of drip washing goes out ammoniacal liquor as the charging of neutralization reactor ammoniacal liquor; Filter cake drying device heat drying steams ammonia and returns neutralization reactor after the drip washing, and the solid drying thing is the ferric oxide mixture that contains small amount of impurities, can be back to iron-smelting raw material.
Process flow sheet of the present invention as shown in drawings, the spent pickle liquor concentration scope of application is at weight percent 10～30%.
Advantage of the present invention is:
The present invention recycles useful resources in administering the process of polluting fully, does not have any wasting of resources;
The usage quantity of ammonium sulfate, iron oxide product is big, can be digested by other commercial runs fully;
The ammonium sulfate product quality of producing is good, can satisfy agricultural fertile needs standard;
The utilization ratio of whole process ammonia resource is more than 90%, the resource utilization height.
Description of drawings
Fig. 1: process flow sheet of the present invention
Embodiment
Embodiment 1: the spent pickle liquor of the ferrous and sour weight percent 25% of sulfur waste of sulfur acid, remove solid particle polluter by primary filter after, waste liquid enters neutralization reactor; Before carrying out, neutralization reaction adds polyacrylamide solution, making polyacrylamide concentration in waste liquid is 100ppm (being weight percent 0.01%), the ammoniacal liquor that under agitation adds ammonia weight percent 25% then neutralizes, the pH value of neutralization reaction reaches at 8.5 o'clock, adds deposition filter and carries out filtering separation.Filtrate is heated to 90 ℃, and constant temperature 10 minutes, and then filtering and impurity removing; The secondary filtrate is through evaporation, crystallization, and the ammonium sulfate color and luster that obtains is pure white, the ferro element weight percent 0.00047% of crystalline product.Quality product is good.
Filter cake volume after the filtration is 56% of a former waste liquid volume, and the ammoniacal liquor of the ammonia weight percent 25% of adding and former waste liquid equal volume carries out drip washing to filter cake and filters, and then with filter cake thermal dehydration and drying, the ammonium sulfate weight content of dry back filter cake is 6.7%.When leachate was back to neutralization reactor with the evaporation ammonia, the ammonia utilization ratio of whole flow process was 86.5%, and the ammonia utilization ratio is higher.
Embodiment 2: the spent pickle liquor of the ferrous and sour weight percent 10% of sulfur waste of sulfur acid, remove solid particle polluter by primary filter after, waste liquid enters neutralization reactor; Before carrying out, neutralization reaction adds polyacrylamide solution, making polyacrylamide concentration in waste liquid is 500ppm (being weight percent 0.05%), the ammoniacal liquor that under agitation adds ammonia weight percent 25% then neutralizes, the pH value of neutralization reaction reaches at 11.5 o'clock, adds deposition filter and carries out filtering separation.Filtrate is heated to 60 ℃, and constant temperature 60 minutes, and then filtering and impurity removing; The secondary filtrate is through evaporation, crystallization, and the ammonium sulfate color and luster that obtains is pure white, the ferro element weight percent 0.0016% of crystalline product.Quality product is better.Filter cake volume after the filtration is 51% of a former waste liquid volume, and the ammoniacal liquor of the ammonia weight percent 25% of adding and former waste liquid equal volume carries out drip washing to filter cake and filters, and then with filter cake thermal dehydration and drying, the ammonium sulfate weight content of dry back filter cake is 4.7%.When leachate was back to neutralization reactor with the evaporation ammonia, the ammonia utilization ratio of whole flow process was 90.4%, and the ammonia utilization ratio is higher.
Embodiment 3: the spent pickle liquor of the ferrous and sour weight percent 30% of sulfur waste of sulfur acid, remove solid particle polluter by primary filter after, waste liquid enters neutralization reactor; Before carrying out, neutralization reaction adds sodium polyacrylate solution, making sodium polyacrylate concentration in waste liquid is 50ppm (being weight percent 0.005%), the ammoniacal liquor that under agitation adds ammonia weight percent 25% then neutralizes, the pH value of neutralization reaction reaches at 8 o'clock, adds deposition filter and carries out filtering separation.In confined conditions, filtrate is heated to 105 ℃, and constant temperature 5 minutes, and then filtering and impurity removing; The secondary filtrate is through evaporation, crystallization, and the ammonium sulfate color and luster that obtains is pure white, the ferro element weight percent 0.0009% of crystalline product.Quality product is better.
Filter cake volume after the filtration is 47% of a former waste liquid volume, and the ammoniacal liquor of the ammonia weight percent 25% of adding and former waste liquid equal volume carries out drip washing to filter cake and filters, and then with filter cake thermal dehydration and drying, the ammonium sulfate weight content of dry back filter cake is 3.7%.When leachate was back to neutralization reactor with the evaporation ammonia, the ammonia utilization ratio of whole flow process was 91.9%, and the ammonia utilization ratio is higher.
Embodiment 4: the spent pickle liquor of the ferrous and sour weight percent 25% of sulfur waste of sulfur acid, remove solid particle polluter by primary filter after, waste liquid enters neutralization reactor; Before carrying out, neutralization reaction adds polyethylene benzene sulfonic acid sodium salt solution, making polyethylene benzene sulfonic acid sodium salt concentration in waste liquid is 100ppm (being weight percent 0.01%), the ammoniacal liquor that under agitation adds ammonia weight percent 25% then neutralizes, the pH value of neutralization reaction reaches at 8 o'clock, adds deposition filter and carries out filtering separation.Filtrate is heated to 90 ℃, and constant temperature 20 minutes, and then filtering and impurity removing; The secondary filtrate is through evaporation, crystallization, and the ammonium sulfate color and luster that obtains is pure white, the ferro element weight percent 0.0009% of crystalline product.Quality product is better.
Filter cake volume after the filtration is 40% of a former waste liquid volume, and the ammoniacal liquor of the ammonia weight percent 25% of adding and former waste liquid equal volume carries out drip washing to filter cake and filters, and then with filter cake thermal dehydration and drying, the ammonium sulfate weight content of dry back filter cake is 3.2%.When leachate was back to neutralization reactor with the evaporation ammonia, the ammonia utilization ratio of whole flow process was 93.8%, and the ammonia utilization ratio is higher.
The spent pickle liquor of the ferrous and sour weight percent 25% of sulfur waste of sulfur acid, step according to embodiment 1, under other identical conditions, carry out no flocculation agent, 100ppm polyacrylamide, the 100ppm sodium polyacrylate of 100 milliliters of waste liquids, the comparison filtration test of 100ppm polyethylene benzene sulfonic acid sodium salt flocculation agent respectively.Four filter the deadline was respectively 45,38,35,33 minutes, and the filtrate volume is respectively: 40,48,55,60, and organic floculant has obviously improved solid-liquid separation effect.
Claims (3)
1. the method for reclaim(ed) sulfuric acid ammonium and ferric oxide from a sulfuric acid pickling waste liquid is characterized in that, may further comprise the steps:
At first spent pickle liquor filter to be removed solid particle polluter by primary filter, and waste liquid enters neutralization reactor then, in neutralization reactor with the aqueous solution and the ammonia generation neutralization reaction of ammonia, when pH value in reaction 8～11.5 the time, form precipitation more fully;
Carrying out in neutralization reaction that the stage adds with respect to the waste liquid weight percent is 0.005%～0.05% organic floculant, and the input deposition filter carries out filtering separation; After the heating of the filtrate of deposition filter, through the filtering and impurity removing once more of filter again; Filter residue is discharged to deposition filter, and the secondary filtrate is evaporated in evaporative crystallizer, crystallization, obtains the pure white ammonium sulfate of color and luster;
With the aqueous solution drip washing of ammonia, the drop of drip washing goes out the aqueous solution charging of the aqueous solution of ammonia as neutralization reactor ammonia to the filter cake of deposition filter in leaching device; Filter cake drying device heat drying steams ammonia and returns neutralization reactor after the drip washing, and the solid drying thing is the ferric oxide mixture that contains small amount of impurities.
2. method according to claim 1 is characterized in that organic floculant is selected one of polyacrylamide, sodium polyacrylate, polyethylene benzene sulfonic acid sodium salt for use.
3. method according to claim 1 is characterized in that the filtrate Heating temperature of deposition filter is 60-105 ℃, and keeps 5-60 minute.
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| CN2007101767415A CN101177284B (en) | 2007-11-02 | 2007-11-02 | Method for reclaiming sulfuric ammonium and ferric oxide from sulfuric acid pickling waste fluid |
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| CN101177284B true CN101177284B (en) | 2010-06-02 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376547B (en) * | 2008-10-10 | 2010-10-13 | 韩晓波 | Method for recovering and processing pickling solution of refining benzene |
| CN102602962A (en) * | 2012-04-13 | 2012-07-25 | 瓮福（集团）有限责任公司 | Method for preparing ammonium sulfate by use of dilute acid generated by pyrite-based acid production |
| CN103073140B (en) * | 2012-11-22 | 2015-01-14 | 南阳理工学院 | Flocculation deposition-evaporation-membrane separation combined technology for processing maleic anhydride industrial acidic waste water |
| CN103318918B (en) * | 2013-05-14 | 2016-01-13 | 武汉百富环保工程有限公司 | A kind of method of purifying and recovering ammonia gas |
| CN104743725B (en) * | 2013-12-30 | 2017-04-12 | 西南大学 | Sodium saccharin wastewater and similar wastewater treatment method |
| CN105366862A (en) * | 2015-11-18 | 2016-03-02 | 浙江闰土研究院有限公司 | Treatment method of sulfur acid-containing dye wastewater |
| CN109399667A (en) * | 2018-12-14 | 2019-03-01 | 湖南江冶机电科技股份有限公司 | A kind of method and equipment of lead plaster ammonium method desulfurizing byproduct-ammonium sulfate deep purifying |
| CN110482740B (en) * | 2019-08-16 | 2023-09-01 | 联峰钢铁（张家港）有限公司 | Sewage acid treatment method |
| CN114950005A (en) * | 2022-06-29 | 2022-08-30 | 格林爱科(荆门)新能源材料有限公司 | Recovery system and recovery method for ternary positive electrode precursor production regeneration waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1994702A (en) * | 1933-02-23 | 1935-03-19 | Arch W Harris | Utilization of waste pickling acids |
| CN87103373A (en) * | 1987-05-06 | 1988-11-23 | 黄卓林 | Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor |
| CN1056668A (en) * | 1991-07-06 | 1991-12-04 | 范钦英 | Make the method for iron oxide yellow with iron washing acid pickle |
| CN1180662A (en) * | 1996-10-24 | 1998-05-06 | 冶金工业部长沙矿冶研究院 | Continuous production of high-purity iron oxide and device thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1994702A (en) * | 1933-02-23 | 1935-03-19 | Arch W Harris | Utilization of waste pickling acids |
| CN87103373A (en) * | 1987-05-06 | 1988-11-23 | 黄卓林 | Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor |
| CN1056668A (en) * | 1991-07-06 | 1991-12-04 | 范钦英 | Make the method for iron oxide yellow with iron washing acid pickle |
| CN1180662A (en) * | 1996-10-24 | 1998-05-06 | 冶金工业部长沙矿冶研究院 | Continuous production of high-purity iron oxide and device thereof |
Non-Patent Citations (2)
| Title |
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| 黄若飞.工业废酸液处理及综合利用技术.化学工程师110 11.2004,110(11),25-26. |
| 黄若飞.工业废酸液处理及综合利用技术.化学工程师110 11.2004,110(11),25-26. * |
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