CN102828192A - Resourceful treatment method for pickling waste liquor in steel industry - Google Patents
Resourceful treatment method for pickling waste liquor in steel industry Download PDFInfo
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- CN102828192A CN102828192A CN2012103117728A CN201210311772A CN102828192A CN 102828192 A CN102828192 A CN 102828192A CN 2012103117728 A CN2012103117728 A CN 2012103117728A CN 201210311772 A CN201210311772 A CN 201210311772A CN 102828192 A CN102828192 A CN 102828192A
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- sulfuric acid
- acid
- ferrous sulfate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recycling sulfuric acid and ferrous sulfate from pickling waste liquor in the steel industry, and belongs to the technical field of resourceful treatment for waste liquor. The method mainly includes a technology for recycling ferrous sulfate by a freezing crystallization method, a technology for recycling sulfuric acid by a strong caustic anion exchange resin acid blocking principle and a technology for preparing polymeric ferric sulfate by a one-step catalysis method. The method has the advantages that the process and operation are simple, secondary pollution is prevented, resourceful treatment for the sulfuric acid pickling waste liquor is realized, the sulfuric acid is recycled and can be used for production, the ferrous sulfate is also recycled, polymeric ferric sulfate water purifier is prepared, and zero pollution emission of a steel enterprise is realized; recovery rates of the sulfuric acid and the ferrous sulfate are high and reach 82% and 97% respectively; and the quality of the polymeric ferric sulfate water purifier meets a type-I standard of the Polymeric Ferric Sulfate Water Purifier (GB14591-2006).
Description
Technical field
The invention belongs to the effluent resource processing technology field, be specifically related to reclaim the method for sulfuric acid and ferrous sulfate in the steel industry spent pickle liquor.
Background technology
Steel pipe all need adopt the method for pickling to remove its surperficial zone of oxidation before use, and the condition of pickling is that sulfuric acid concentration is 20～25%, and the temperature of pickling is 50～65 ℃.Sulfuric acid concentration is lower than 5% in pickle solution, when ferrous sulfate concentration reaches 250g/L, just can not satisfy production requirement, needs to change pickle solution, and the pickle solution that changes is exactly usually said spent pickle liquor.Because serious corrodibility is put into " national Hazardous wastes register ".
Steel industry (sulfuric acid) spent pickle liquor treatment technology mainly contains 7 big class methods at present.
1. neutralizing treatment method: generally adopt lime, carbide slag or caustic soda that it is carried out neutralizing treatment, discharge after making the pH value reach discharging standards.Neutralisation is simple and easy to do, but manages loaded down with trivial details waywardly, and the spent acid treatment capacity is restricted, and the sulfuric acid in the spent pickle liquor, FeSO
4Be not utilized effectively etc. resource.When the processing unit of iron and steel enterprise's spent pickle liquor,, can consider to utilize acid-base waste fluid to neutralize each other when nearer with the spent lye treatment unit distance of other enterprises, reach the purpose of controlling " giving up " with " giving up ".
Its shortcoming is when spent acid amount and concentration change are big, and treatment effect often is difficult to guarantee, need sets up equalizing tank or additional neutralizing agent.
2. crystallization process: the crystallization reclaim(ed) sulfuric acid is ferrous to have 3 kinds of methods usually:
1. spent pickle liquor is cooled to-5～10 ℃, most of ferrous sulfate is with FeSO
47H
2The O crystalline form is separated out;
2. spent pickle liquor through heat concentrate after, be cooled to normal temperature (20～25 ℃), ferrous sulfate is with FeSO
47H
2The O crystal is separated out; 3. in spent pickle liquor, add sulfuric acid in order to the ferrous sulfate of saltouing, separate out FeSO
47H
2The O crystal.
Reduce the ferrous cost of reclaim(ed) sulfuric acid and raise the efficiency, employing sulfuric acid is saltoutd and suitable cooling way of combining is cost-effective.
3. nanofiltration membrane separation: this technology mainly is to utilize nf membrane different to the rejection of sulfuric acid and ferrous sulfate; Under the effect of pressure; The macromole ferrous sulfate hydrate is trapped in a side of film, and lets micromolecular sulfuric acid see through film, realize both separation; To the concentrated mother liquor processing of lowering the temperature, make ferrous sulfate hydrate form crystallization and separate out then.The nanofiltration membrane separation technology has that film body is heat-resisting, acid-proof alkaline good, working pressure is low, collection concentrates and dialysis is characteristics such as one.
The nanofiltration membrane separation method is only used under the bigger occasion of spent pickle liquor rate ratio, just has certain economic property.This mainly is because the nanofiltration membrane separation method needs higher equipment input, and higher energy consumption is also arranged in operational process, only reach certain treatment scale after, just can realize balance between revenue and expenditure.
4. electroosmose process: the key of electroosmose process recovered acid is selecting for use of ion-exchange membrane, generally anion-exchange film, H
+See through easily, current efficiency is lower, therefore should adopt H
+Difficult perviousness anionic membrane is to improve current efficiency; In addition, during recovered acid, metals ion also can see through cationic exchange membrane from the acid waste liquid that contains metals ion, can select the monovalent ion exchange membrane for use when therefore selecting cationic exchange membrane for use, with the purity of further raising recovered acid.Electroosmose process also can reclaim the sulfuric acid in the spent pickle liquor, and extracts iron wherein.The advantage of this method is that equipment is simple, and organic efficiency is high; Shortcoming is that current consumption is too high.
5. iron filings method: this method places a reactive tank fully react sulfuric acid waste and iron filings earlier, again solution is heated to 100 ℃, reaction 2h, and naturally cooling after heating is concentrated is separated out the ferrous sulfate crystallization, is dried by centrifuge dewatering at last.
The iron filings method can reclaim basic, normal, high three grade ferrous sulfates from pickling waste waters, supply industrial or agricultural, medicine, chemical reagent to use.Have advantages such as simple to operation, less investment, expense are low, but can only reclaim(ed) sulfuric acid ferrous, can not reclaim(ed) sulfuric acid, processing power is little, and raffinate needs to handle again; Poor product quality, production cycle are long, are applicable to that the discharging of waste liquid amount is little, Fe
2+The processing of the medium and small iron and steel enterprise sulfuric acid washing waste water that content is higher.
6. biological process: common oxidation spent pickle liquor method is all carried out under the pH conditions of higher.Foreign study is the result show, can utilize mikrobe sulphur microbacterium (microbacteria) oxidation divalent iron salt, and then hydrolysis generates yellow ammonium ferrovanadium, FeOHSO
4And α-Fe
2O
3An advantage of this biological oxidation process is exactly under very low pH, to carry out, and can be low to moderate pH=1.4 ~ 1.5 usually.This method need be at NH
4 +Could carry out smoothly under the condition that exists.
In the liquid of handling, the mass concentration of remaining iron ion is low to moderate 0.2g/L, and vitriolic concentration has been higher than original sour scouring water (0.3mol/L), so can directly come back to pickling lines, recycle.
7. complete absorption method-Lu Zi nanofarad: spent acid solution concentrates through the decompression heating evaporation, and its slurries send into reactor drum and HC1 gas reacts by following formula: FeSO
4+ 2HC1 → H
2SO
4+ FeCl
2↓.Because FeCl
2In concentrated sulfuric acid solution, do not dissolve and crystalline deposit, can make H like this
2SO
4Separate with iron.Thereby be used for the H of pickling
2SO
4Can all turn back to pickling process and utilize again, and FeCl
2Crystallization then is used to produce Fe
2O
3Powder.The technology of having improved is with FeCl
2Solution is directly injected in the stove of heating more than 600 ℃, Fe
2O
3Powder is discharged from furnace bottom, and HCl gas turns back in the reactor drum and recycles.α-the Fe that uses this method to produce
2O
3Powder purity can reach 99.3%, is the main raw material of ferrite magnetic material.
The shortcoming of this method is: in order to obtain the α-Fe of higher degree
2O
3, must make with extra care spent acid solution in advance, and this technology required equipment investment being high, the maintenance management difficulty is big.
Above-mentioned technology is equal existing problems separately, and secondary pollution, equipment corrosion are serious as producing, complex process, operation easier is big, investment is big, working cost is high, floor space is big etc.It is limited that these factors make prior art apply.
Summary of the invention
Advantages such as the present invention provides the recycling processing method of a kind of steel industry (sulfuric acid) spent pickle liquor, and this method has recovery height, and technology is simple, and cost is low, and environmental pollution is little.
Method of the present invention comprises: the ferrous technology of freeze crystallization reclaim(ed) sulfuric acid; Strongly basic anion exchange resin acid retardance principle reclaim(ed) sulfuric acid technology; One step catalysis method is produced the bodied ferric sulfate technology.
1. ferrous sulfate recovery technology: spent pickle liquor introduced the freezing and crystallizing jar cools off, crystallization, opens baiting valve after for some time, with whizzer carry out salt, acid separates, it is for use to separate the iron vitriol that obtains.
2. sulfuric acid recovery technology: the acid behind the above-mentioned desalination through strongly basic anion exchange resin, is utilized acid retardance technology, acid is wherein blocked, and ferrous sulfate can pass through smoothly, uses water elution then, the sulfuric acid of recovery returns the pickle house complex acid and uses.
3. bodied ferric sulfate technology of preparing: the ferrous sulfate that separation is obtained is dissolved in the above-mentioned resin flow fluid, under stirring condition, slowly drips the catalyzer and the vitriol oil, until obtaining the reddish-brown transparent liquid, is bodied ferric sulfate (PFS).
A kind of preferred version of the present invention is:
1. ferrous sulfate recovery technology
1) cooling, crystallisation process: spent pickle liquor introduced the freezing and crystallizing jar cools off, crystallization, supporting electrolyte water temp-18 ℃, the freezing and crystallizing temperature of employing is-7～-9 ℃, every jar of freezing time 1.5～2.0h.
2) sepn process: carry out salt, acid separation with whizzer, centrifuge speed 750～900 commentaries on classics/min, centrifugation time are 30min.
2. sulfuric acid recovery technology
1) adsorption process: through strongly basic anion exchange resin, feed liquor stops the spent pickle liquor that above-mentioned separation is obtained after 10 BV with the flow velocity of 10mL/min.
2) desorption process: adopt zero(ppm) water that resin is carried out desorption and regeneration, regeneration ending after 15 BV, desorption liquid is a dilute sulphuric acid, returns the pickle house complex acid and uses.
3. bodied ferric sulfate technology of preparing
Under the condition of continuously stirring, in the sulphuric acid soln of ferrous sulfate, slowly drip the ydrogen peroxide 50 and the vitriol oil, the dosage of ydrogen peroxide 50 is nH
2O
2: nFe
2+=1:2, vitriolic dosage are nH
2SO
4: nFe
2+=1:3, the reaction times is 1～1.2h, just can obtain the reddish-brown transparent liquid, i.e. bodied ferric sulfate (PFS).
1), technology is simple the present invention has the following advantages:, easy handling can not cause secondary pollution; Realized recycling treatment to sulfuric acid pickling waste liquid; Both reclaim sulfuric acid, can be back to production, reclaimed ferrous sulfate again; Make the water purification agent bodied ferric sulfate, realized the zero release that iron and steel enterprise pollutes; 2), the recovery of sulfuric acid, ferrous sulfate is high, reached 82% and 97% respectively; 3) the polyaluminum sulfate weight of iron reaches " water purification agent bodied ferric sulfate " (GB14591-2006) I type standard.
Embodiment
The embodiment that below only provides for explanation the present invention, further details of the present invention and advantage will become clearer.Need to prove that these embodiment are used to limit protection scope of the present invention.
What adopt among the embodiment is certain iron and steel enterprise's sulfuric acid pickling waste liquid, contains the ferrous sulfate of 5% sulfuric acid and 220～250g/L in every liter of waste liquid approximately.Result of implementation is seen table 1.
Embodiment 1:
Through strongly basic anion exchange resin, feed liquor stops the spent pickle liquor that above-mentioned separation is obtained after 10 BV with the flow velocity of 10mL/min; Adopt zero(ppm) water that resin is carried out desorption and regeneration, regeneration ending after 15 BV, desorption liquid is a dilute sulphuric acid, returns the pickle house complex acid and uses.The sulfuric acid recovery is 82.4%.
Embodiment 2:
Through strongly basic anion exchange resin, feed liquor stops the spent pickle liquor that above-mentioned separation is obtained after 11 BV with the flow velocity of 10mL/min; Adopt zero(ppm) water that resin is carried out desorption and regeneration, regeneration ending after 15 BV, desorption liquid is a dilute sulphuric acid, returns the pickle house complex acid and uses.The sulfuric acid recovery is 82.7%.
Embodiment 3:
Through strongly basic anion exchange resin, feed liquor stops the spent pickle liquor that above-mentioned separation is obtained after 9 BV with the flow velocity of 10mL/min; Adopt zero(ppm) water that resin is carried out desorption and regeneration, regeneration ending after 15 BV, desorption liquid is a dilute sulphuric acid, returns the pickle house complex acid and uses.The sulfuric acid recovery is 80.4%.
Table 1 test-results
| Embodiment | Adsorption volume (BV) | Desorption volume (BV) | The recovery (%) |
| 1 | 10 | 15 | 82.4 |
| 2 | 11 | 15 | 82.7 |
| 3 | 9 | 15 | 80.4 |
Can find out that by table 1 present method recovery is high and stable, can reach more than 82.4%; Can not produce any secondary pollution.
What adopt among the embodiment is certain iron and steel enterprise's sulfuric acid pickling waste liquid, contains the ferrous sulfate of 5% sulfuric acid and 220～250g/L in every liter of waste liquid approximately.Result of implementation is seen table 2.
Embodiment 4:
(about 25 ℃) add FeSO under the room temperature condition in the 100mL there-necked flask
47H
2O and H
2SO
4Mixture, wherein FeSO
47H
2O50g; H
2SO
4And H
2O
2Take the mode that drips, H
2SO
4Consumption 3.5mL; H
2O
2Consumption 10.0mL, stirring makes it to mix fully, and reaction 1.5h obtains the reddish-brown transparent liquid, i.e. and the full iron amount of product polyaluminum sulfate (PFS), and product quality indicator, basicity no longer include variation basically.
Embodiment 5:
(about 25 ℃) add FeSO under the room temperature condition in the 100mL there-necked flask
47H
2O and H
2SO
4Mixture, wherein FeSO
47H
2O50g; H
2SO
4And H
2O
2Take the mode that drips, H
2SO
4Consumption 4.0mL; H
2O
2Consumption 12.0mL, stirring makes it to mix fully, and reaction 1.5h obtains the reddish-brown transparent liquid, i.e. and the full iron amount of product polyaluminum sulfate (PFS), and product quality indicator, basicity no longer include variation basically.
Embodiment 6:
(about 25 ℃) add FeSO under the room temperature condition in the 100mL there-necked flask
47H
2O and H
2SO
4Mixture, wherein FeSO
47H
2O50g; H
2SO
4And H
2O
2Take the mode that drips, H
2SO
4Consumption 4.5mL; H
2O
2Consumption 15.0mL, stirring makes it to mix fully, and reaction 1.5h obtains the reddish-brown transparent liquid, i.e. and the full iron amount of product polyaluminum sulfate (PFS), and product quality indicator, basicity no longer include variation basically.
Table 2 test-results
| Embodiment | H 2SO 4Consumption (mL) | H 2O 2Consumption (mL) | The PFS quality |
| 4 | 3.5 | 10.0 | Fe 2+Content and basicity all meet first grade standard (Fe 2+Massfraction<=0.1%, basicity>;=12) |
| 5 | 4.0 | 12.0 | Fe 2+Content and basicity all meet first grade standard (Fe 2+Massfraction<=0.1%, basicity>;=12) |
| 6 | 4.5 | 15.0 | Fe 2+Content and basicity all meet first grade standard (Fe 2+Massfraction<=0.1%, basicity>;=12) |
Can find out that by table 2 present method productive rate is high and stable, can not produce any secondary pollution.
Claims (5)
1. the recycling processing method of a steel industry spent pickle liquor is characterized in that comprising following consecutive steps:
A) spent pickle liquor is introduced the freezing and crystallizing jar cools off, crystallization;
B) carry out salt, acid separation with whizzer;
C) strongly basic anion exchange resin is passed through in the acid behind the above-mentioned desalination, use the zero(ppm) water wash-out then, the sulfuric acid of recovery returns the pickle house complex acid and uses;
D) ferrous sulfate that separation is obtained is dissolved in the above-mentioned resin flow fluid, under stirring condition, adds the catalyzer and the vitriol oil, until obtaining the reddish-brown transparent liquid, is bodied ferric sulfate PFS.
2. the method for claim 1 is characterized in that in the step a), supporting electrolyte water temp-18 ℃, and the freezing and crystallizing temperature of employing is-7～-9 ℃, every jar of freezing time 1.5～2.0h.
3. the method for claim 1 is characterized in that in the step b), and centrifuge speed 750～900 commentaries on classics/min, centrifugation time are 30min.
4. the method for claim 1 is characterized in that in the step c), and the acid behind the desalination is 10mL/min through the flow velocity of strongly basic anion exchange resin, and feed liquor stops after 10 BV; Adopt zero(ppm) water that resin is carried out desorption and regeneration, regeneration is accomplished after 15 BV.
5. the method for claim 1 is characterized in that in the step d), and catalyzer is a ydrogen peroxide 50, and the dosage of ydrogen peroxide 50 is nH
2O
2: nFe
2+=1:2, vitriolic dosage are nH
2SO
4: nFe
2+=1:3, the reaction times is 1～1.2h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN105152229A (en) * | 2015-07-31 | 2015-12-16 | 上海安赐机械设备有限公司 | High-density ferrous sulphate-containing waste sulfuric acid purification and recovery system and recovery process thereof |
| CN105329953A (en) * | 2015-12-02 | 2016-02-17 | 浙江奇彩环境科技有限公司 | Titanium white waste acid resourceful treatment technology |
| CN105776354A (en) * | 2014-12-22 | 2016-07-20 | 祐鼎（福建）光电材料有限公司 | Preparation method of polymeric ferric sulfate |
| CN108046336A (en) * | 2018-01-02 | 2018-05-18 | 张家港洁利环保科技有限公司 | The industrial process of green vitriol crystal |
| CN108147471A (en) * | 2018-01-02 | 2018-06-12 | 张家港洁利环保科技有限公司 | The industrial process of Feromax crystal |
| CN109167059A (en) * | 2018-08-07 | 2019-01-08 | 陈子清 | A method of lithium carbonate is prepared using waste lithium iron phosphate battery |
| CN112794292A (en) * | 2021-04-15 | 2021-05-14 | 杭州水处理技术研究开发中心有限公司 | Method and system for purifying and recycling waste sulfuric acid |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276402A (en) * | 2013-05-21 | 2013-09-04 | 山西大学 | Method for treating waste liquor obtained in pickling of hot-rolled chromium stainless steel wire rod by using sulfuric acid process |
| CN105776354A (en) * | 2014-12-22 | 2016-07-20 | 祐鼎（福建）光电材料有限公司 | Preparation method of polymeric ferric sulfate |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN105152229A (en) * | 2015-07-31 | 2015-12-16 | 上海安赐机械设备有限公司 | High-density ferrous sulphate-containing waste sulfuric acid purification and recovery system and recovery process thereof |
| CN105329953A (en) * | 2015-12-02 | 2016-02-17 | 浙江奇彩环境科技有限公司 | Titanium white waste acid resourceful treatment technology |
| CN108046336A (en) * | 2018-01-02 | 2018-05-18 | 张家港洁利环保科技有限公司 | The industrial process of green vitriol crystal |
| CN108147471A (en) * | 2018-01-02 | 2018-06-12 | 张家港洁利环保科技有限公司 | The industrial process of Feromax crystal |
| CN109167059A (en) * | 2018-08-07 | 2019-01-08 | 陈子清 | A method of lithium carbonate is prepared using waste lithium iron phosphate battery |
| CN112794292A (en) * | 2021-04-15 | 2021-05-14 | 杭州水处理技术研究开发中心有限公司 | Method and system for purifying and recycling waste sulfuric acid |
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Application publication date: 20121219 |