CN105600836A - Method for recycling useful ingredients in acid pickling waste liquid - Google Patents
Method for recycling useful ingredients in acid pickling waste liquid Download PDFInfo
- Publication number
- CN105600836A CN105600836A CN201610047292.3A CN201610047292A CN105600836A CN 105600836 A CN105600836 A CN 105600836A CN 201610047292 A CN201610047292 A CN 201610047292A CN 105600836 A CN105600836 A CN 105600836A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- acid
- hydrochloric acid
- concentration
- cooled
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
Abstract
A method for recycling useful ingredients in acid pickling waste liquid includes the following steps that firstly, concentrated hydrochloric acid is added into hydrochloric acid pickling waste liquid or concentrated sulfuric acid is added into sulfuric acid pickling waste liquid, and the hydrochloric acid mass concentration or the sulfuric acid mass concentration of the waste liquid is adjusted to be 20-25%; secondly, the temperature of the waste liquid with the acid concentration adjusted is lowered to be 0-3 DEG C, and ferrous chloride and ferrous sulfate crystals in the waste liquid precipitate; thirdly, the precipitated ferrous chloride and ferrous sulfate crystals are separated out of the waste liquid. By means of the method, the useful ingredients in the acid pickling waste liquid can be recycled, cost is effectively saved, zero discharge of acid pickling waste liquid can also be achieved, and pollution of the acid pickling waste liquid to the environment is avoided.
Description
Technical field
The present invention relates to the recovery method of useful component in a kind of pickle liquor.
Background technology
Pickle liquor is the oxide in order to remove steel surface, adopts acid to carry out the waste liquid producing when acid wash is processed steel, and waste liquid multi-source is in steel plant, Electroplate Factory and machining factory etc.
The oxide main component of steel surface is the oxide of iron, and in the time that these oxides are immersed in acid solution, these oxides can react with acid, generate the salt of water-soluble or acid solution, thereby these oxides are removed from steel surface. The acid that pickling adopts is mainly hydrochloric acid or sulfuric acid.
Pickling is that steel are processed requisite processing step, and very large shortcoming of this technique is exactly to produce a large amount of pickle liquors. Conventionally in pickle liquor, hydrochloric acid or sulfuric acid content are 3～10%, as deal carefully with, and are great environment hidden danger.
At present, the modal processing method of pickle liquor is neutralisation, but the method not only cannot Recycling of waste liquid in useful composition, also need to consume a large amount of alkaline matters as nertralizer, and in the process disposing waste liquid, can produce a large amount of solid waste, cause secondary pollution.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiency of above-mentioned background technology, provides the one can be effectively cost-saving, realizes the zero-emission of pickle liquor, avoids the recovery method of pickle liquor to useful component in the pickle liquor of environment.
The technical scheme that the present invention solves its technical problem employing is that the recovery method of useful component in a kind of pickle liquor, comprises the following steps:
(1) in hydrochloric acid pickling waste liquor, add concentrated hydrochloric acid or add the concentrated sulfuric acid in sulfuric acid pickling waste liquid, hydrochloric acid mass concentration or the h 2 so 4 concentration of waste liquid are adjusted to 20%-25%;
(2) waste liquid that regulates acid concentration is cooled to 0-3 DEG C, frerrous chloride or ferrous sulfate crystallization are wherein separated out;
(3) frerrous chloride crystallization or the ferrous sulfate crystallization of separating out are separated from waste liquid.
Further, in step (1), the hydrochloric acid after adjusting or the mass concentration of sulfuric acid are 21%-24%.
Further, in step (1), the hydrochloric acid after adjusting or the mass concentration of sulfuric acid are 22%-23%.
Further, in step (2), first the waste liquid that regulates acid concentration is left standstill and is cooled to room temperature; Again the waste liquid that is cooled to room temperature is cooled to 0-3 DEG C.
Further, in step (2), the waste liquid that regulates acid concentration is cooled to 1-2 DEG C.
Utilizing gained frerrous chloride of the present invention crystallization or ferrous sulfate crystallization, is technical grade frerrous chloride or ferrous sulfate; Reclaim hydrochloric acid acid solution or sulfuric acid acid solution after frerrous chloride crystallization or ferrous sulfate crystallization, can be recycled and reused for the pickling of steel.
Compared with prior art, advantage of the present invention is as follows: can reclaim the useful component in pickle liquor, and effectively cost-saving; Realize the zero-emission of pickle liquor, avoid pickle liquor to environment.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment comprises the following steps:
(1) in hydrochloric acid pickling waste liquor, add concentrated hydrochloric acid, the hydrochloric acid mass concentration of acid pickle is adjusted to 25%;
(2) waste liquid that regulates acid concentration is left standstill and is cooled to room temperature;
(3) waste liquid that is cooled to room temperature is carried out to frozen cooling by refrigerator, the temperature of waste liquid is reduced to 0 DEG C, frerrous chloride formation crystal of hydrate is wherein separated out;
(4) by the frerrous chloride crystal of hydrate of separating out from acid pickle centrifugation out, the frerrous chloride that gained frerrous chloride crystal of hydrate is technical grade.
Reclaim the hydrochloric acid acid solution after frerrous chloride, be recycled and reused for the pickling of steel.
Certain steel tube factory, approximately 5000 tons of year generation pickle liquors, hydrochloric about 10wt% in waste liquid. Utilize the inventive method to reclaim useful component wherein. Retracting device is invested approximately 600,000 yuan, after retracting device operation, reclaims then approximately 600 tons of frerrous chlorides, and approximately 2000 tons, the watery hydrochloric acid of mass concentration 25% left and right, has regained cost of investment then, not only for enterprise has created certain economic worth; Can also realize the zero-emission of pickle liquor, be outer row's disposal cost of enterprise's saving pickle liquor.
Embodiment 2
The present embodiment comprises the following steps:
(1) in sulfuric acid pickling waste liquid, add the concentrated sulfuric acid, the h 2 so 4 concentration of acid pickle is adjusted to 20%;
(2) waste liquid that regulates acid concentration is left standstill and is cooled to room temperature;
(3) waste liquid that is cooled to room temperature is carried out to frozen cooling by refrigerator, the temperature of waste liquid is reduced to 3 DEG C, ferrous sulfate formation crystal of hydrate is wherein separated out;
(4) by the ferrous sulfate hydrate crystallization of separating out from waste liquid centrifugation out, the ferrous sulfate that the ferrous sulfate hydrate crystallization obtaining is technical grade.
Isolate the sulfuric acid acid solution after ferrous sulfate hydrate crystallization, be recycled and reused for the pickling of steel.
Certain machinery enterprise subordinate vehicle bridge factory, approximately 3000 tons of year generation pickle liquors, the about 8wt% of sulfur acid in waste liquid. Utilize the inventive method to reclaim useful component wherein. Retracting device is invested approximately 400,000 yuan, after retracting device operation, and ferrous approximately 360 tons of year reclaim sulfuric acid; Approximately 1200 tons of the dilute sulfuric acids of mass concentration 20% left and right, are recycled and reused for the pickling of steel. Approximately 300,000 yuan of the economic worths of annual recovered material, not only, for enterprise creates economic benefit, can also realize the zero-emission of pickle liquor, are outer row's disposal cost of enterprise's saving pickle liquor.
Those skilled in the art can carry out various modifications and variations to the embodiment of the present invention, if these amendment and modification within the scope of the claims in the present invention and equivalent technologies thereof, these revise and modification also within protection scope of the present invention.
The prior art that the content of not describing in detail in description is known to the skilled person.
Claims (6)
1. a recovery method for useful component in pickle liquor, is characterized in that: comprise the following steps:
(1) in hydrochloric acid pickling waste liquor, add concentrated hydrochloric acid or add the concentrated sulfuric acid in sulfuric acid pickling waste liquid, hydrochloric acid mass concentration or the h 2 so 4 concentration of waste liquid are adjusted to 20%-25%;
(2) waste liquid that regulates acid concentration is cooled to 0-3 DEG C, frerrous chloride or ferrous sulfate crystallization are wherein separated out;
(3) frerrous chloride crystallization or the ferrous sulfate crystallization of separating out are separated from waste liquid.
2. the recovery method of useful component in pickle liquor as claimed in claim 1, is characterized in that: in step (1), the hydrochloric acid after adjusting or the mass concentration of sulfuric acid are 21%-24%.
3. the recovery method of useful component in pickle liquor as claimed in claim 2, is characterized in that: in step (1), the hydrochloric acid after adjusting or the mass concentration of sulfuric acid are 22%-23%.
4. the recovery method of useful component in the pickle liquor as described in one of claim 1-3, is characterized in that: in step (2), first the waste liquid that regulates acid concentration is left standstill and is cooled to room temperature; Again the waste liquid that is cooled to room temperature is cooled to 0-3 DEG C.
5. the recovery method of useful component in the pickle liquor as described in one of claim 1-3, is characterized in that: in step (2), the waste liquid that regulates acid concentration is cooled to 1-2 DEG C.
6. the recovery method of useful component in pickle liquor as claimed in claim 4, is characterized in that: in step (2), the waste liquid that regulates acid concentration is cooled to 1-2 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610047292.3A CN105600836A (en) | 2016-01-25 | 2016-01-25 | Method for recycling useful ingredients in acid pickling waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610047292.3A CN105600836A (en) | 2016-01-25 | 2016-01-25 | Method for recycling useful ingredients in acid pickling waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105600836A true CN105600836A (en) | 2016-05-25 |
Family
ID=55981267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610047292.3A Pending CN105600836A (en) | 2016-01-25 | 2016-01-25 | Method for recycling useful ingredients in acid pickling waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105600836A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046213A (en) * | 2017-12-11 | 2018-05-18 | 珠海绿水环保科技有限公司 | A kind of recovery method of the waste hydrochloric acid of metal ion |
| CN110028041A (en) * | 2019-05-30 | 2019-07-19 | 李永飞 | For handling the waste acidity recovery method and acid-restoring plant of acid washing rolled steel waste liquid |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043535A (en) * | 1988-12-24 | 1990-07-04 | 由正明 | Sulfuric acid pickling waste liquid regenerated processing method |
| CN1164579A (en) * | 1996-05-05 | 1997-11-12 | 大连市金州区环境监测站 | Process for treatment of sulfuric acid pickling waste liquor for pickling steel |
| CN102040196A (en) * | 2009-10-15 | 2011-05-04 | 盐城师范学院 | Method for reclaiming hydrochloric acid and ferrous sulfate from steel hydrochloric acid washing waste liquid |
-
2016
- 2016-01-25 CN CN201610047292.3A patent/CN105600836A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043535A (en) * | 1988-12-24 | 1990-07-04 | 由正明 | Sulfuric acid pickling waste liquid regenerated processing method |
| CN1164579A (en) * | 1996-05-05 | 1997-11-12 | 大连市金州区环境监测站 | Process for treatment of sulfuric acid pickling waste liquor for pickling steel |
| CN102040196A (en) * | 2009-10-15 | 2011-05-04 | 盐城师范学院 | Method for reclaiming hydrochloric acid and ferrous sulfate from steel hydrochloric acid washing waste liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046213A (en) * | 2017-12-11 | 2018-05-18 | 珠海绿水环保科技有限公司 | A kind of recovery method of the waste hydrochloric acid of metal ion |
| CN110028041A (en) * | 2019-05-30 | 2019-07-19 | 李永飞 | For handling the waste acidity recovery method and acid-restoring plant of acid washing rolled steel waste liquid |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102249262B (en) | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater | |
| CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
| CN105585194A (en) | Comprehensive utilization method of high-concentration waste saline water containing Na<+>, Ka<+>, NH<4+>, Cl<->, SO4<2-> and NO<3-> in coal chemical industry | |
| CN105543509A (en) | Method for preparing rare earth chloride from mixed rare earth concentrate or bastnaesite concentrate | |
| CN111018221B (en) | Method for recycling smelting waste acid wastewater | |
| CN103849775B (en) | A kind of method reclaiming nickel and cobalt from high-temperature alloy waste material | |
| CN110550680B (en) | Method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced by sulfuric acid process | |
| CN105600836A (en) | Method for recycling useful ingredients in acid pickling waste liquid | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| FI20196110A (en) | Method for treating pickling acid residue | |
| CN108754158A (en) | A kind of method of copper-contained sludge production cupric sulfate purified | |
| CN104787946B (en) | A kind of wholly-owned source utilization process of steel rolling spent acid | |
| CN105253868B (en) | A kind of organic solvent extraction, recycle prodan mother liquor hydraulic art | |
| CN100357176C (en) | Method for recovering vitriol from waste vitrol containing metal salt | |
| AU3086601A (en) | Regenerating spent pickling liquor | |
| CN105731710A (en) | Comprehensive recycling method of cobalt smelting high-magnesium ammonium sulfate wastewater | |
| CN112981100A (en) | Comprehensive utilization method of red mud by full wet method | |
| CN1884092B (en) | Method for removing calcium ion in zinc sulphate solution | |
| CN101759315A (en) | Method for recycling waste diluted sulfuric acid from steel washing | |
| CN106755997A (en) | A kind of method of nickel-containing ore comprehensive utilization | |
| CN105219957A (en) | A kind of method of Selectively leaching vanadium from bone coal roasting material | |
| CN102764689A (en) | Method for recycling titanium from sulfuric acid method titanium white acidolysis residue | |
| CN104477988B (en) | The recoverying and utilizing method of ferrous sulfate heptahydrate centrifuge mother liquor in sulfate process titanium dioxide production | |
| CN108893774A (en) | A kind of preparation method of metal salt hydrotropy hydrothermal synthesis calcium sulfate crystal whiskers | |
| CN104528910A (en) | Synthetic process of heavy metal chelating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160525 |