CN106167326A - A kind of useless acid treatment process - Google Patents
A kind of useless acid treatment process Download PDFInfo
- Publication number
- CN106167326A CN106167326A CN201610618268.0A CN201610618268A CN106167326A CN 106167326 A CN106167326 A CN 106167326A CN 201610618268 A CN201610618268 A CN 201610618268A CN 106167326 A CN106167326 A CN 106167326A
- Authority
- CN
- China
- Prior art keywords
- acid
- pickle
- delivered
- spent
- ferrous chloride
- 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
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 26
- 238000010306 acid treatment Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 86
- 235000021110 pickles Nutrition 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 23
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 20
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 19
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 10
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The present invention relates to a kind of useless acid treatment process, containing ferrous chloride in described spent acid, comprise the steps: that the acid pickle precipitation that pickling is produced by (1) removes impurity；(2) spent acid after removing impurity is evaporated concentrating, and is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；(4) copperas solution is delivered to regulating reservoir, and adds sulphuric acid (5) acid pickle in regulating reservoir is delivered to crystallisation by cooling tank, continuously stirred acid pickle, until acid pickle not recrystallization；(6) acid pickle after crystallization is delivered to centrifugal separating device and carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and regeneration acid solution.It is an advantage of the current invention that: this process technique can produce high-quality side-product, and the processing cost of reduction spent acid, and the regenerated acid after process can also recycle.
Description
Technical field
The invention belongs to chemical technology field, give up acid treatment process particularly to one.
Background technology
Acid is extensively applied in the industry such as chemical industry, iron and steel.In many production processes, the utilization rate of acid is the lowest, substantial amounts of acid
Go out in company with acid discharge of wastewater.These waste water, as being discharged in environment without process, not only make water body or soil acidification, right
Ecological environment works the mischief, and wastes ample resources.Spent acid and acid waste water are in addition to having acidity, possibly together with substantial amounts of miscellaneous
Matter.
More existing enterprises for above-mentioned phenomenon, have employed fairly simple with containing basic matterial in spent acid and place
Reason, but dehydration it is difficult to too much due to waste residue, easily produce secondary pollution, and cost is the highest, therefore these facilities substantially place
In semiparalysis state.Other major part enterprises all use evaporation concentration method to carry out spent acid process, owing to side-product is of poor quality, market
Narrow, operating cost is the highest, these environmental protection facilities are also had difficulty in taking a step.
Now the spent acid containing ferrous chloride is processed, typically by spent acid evaporation and concentration, add excess the most while hot
Concentrated sulphuric acid, then the absorption of recovered purifying column, the copperas solution of generation is again by calcination process, but this processing method obtains
Side-product quality low.
Therefore, research and development one can produce high-quality side-product, and the spent acid after process can be enable to recycle
Useless acid treatment process be necessary.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of processing cost that can reduce spent acid, and after processing again
Raw acid can also recycle, cost-effective useless acid treatment process.
For solving above-mentioned technical problem, the technical scheme is that a kind of useless acid treatment process, described spent acid contains
Ferrous chloride, its innovative point is: comprise the steps:
(1) impurity is removed through precipitation in being delivered to the acid pickle that pickling produces store up acid pond；
(2) spent acid after removing impurity is evaporated concentrating at a temperature of 50～60 DEG C, makes the ferrous chloride in spent acid contain
Amount raises, and is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；
(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；
(4) copperas solution is delivered to regulating reservoir, and to add sulphuric acid to sulfuric acid concentration be 15%～20%；
(5) acid pickle in regulating reservoir is delivered to crystallisation by cooling tank, continuously stirred acid pickle at a temperature of 0～5 DEG C, until
Acid pickle not recrystallization；
(6) acid pickle after crystallization is delivered to centrifugal separating device carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and
Regeneration acid solution.
Further, in described step (4) regulating reservoir, in spent acid, the concentration of sulphuric acid is 16%～18%.
Further, the speed of described step (5) stirring acid pickle is 60～70 revs/min.
It is an advantage of the current invention that:
(1) the useless acid treatment process of the present invention, it is possible to produce high-quality side-product, and the processing cost of reduction spent acid, and place
Regenerated acid after reason can also recycle；
(2) concentration of sulphuric acid in spent acid is allocated as 15%～20% before crystallisation by cooling by the useless acid treatment process of the present invention, and
During crystallisation by cooling, temperature is controlled at 0～5 DEG C, increase concentrated sulphuric acid concentration and reduction crystallization temperature can make ferrous sulfate
Dissolubility diminish, crystallize out ferrous sulfate crystal grain.
Detailed description of the invention
The following examples can make professional and technical personnel that the present invention is more fully understood, but the most therefore by this
Bright it is limited among described scope of embodiments.
Embodiment 1
The present embodiment gives up acid treatment process, containing ferrous chloride in spent acid, comprises the steps:
(1) impurity is removed through precipitation in being delivered to the acid pickle that pickling produces store up acid pond；
(2) spent acid after removing impurity is evaporated concentrating at a temperature of 60 DEG C, makes the ferrous chloride content liter in spent acid
Height, is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；
(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；
(4) copperas solution is delivered to regulating reservoir, and to add sulphuric acid to sulfuric acid concentration be 15%；
(5) acid pickle in regulating reservoir being delivered to crystallisation by cooling tank, at a temperature of 5 DEG C, the speed with 60 revs/min continues
Stirring acid pickle, until acid pickle not recrystallization；
(6) acid pickle after crystallization is delivered to centrifugal separating device carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and
Regeneration acid solution.
Embodiment 2
The present embodiment gives up acid treatment process, containing ferrous chloride in spent acid, comprises the steps:
(1) impurity is removed through precipitation in being delivered to the acid pickle that pickling produces store up acid pond；
(2) spent acid after removing impurity is evaporated concentrating at a temperature of 50 DEG C, makes the ferrous chloride content liter in spent acid
Height, is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；
(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；
(4) copperas solution is delivered to regulating reservoir, and to add sulphuric acid to sulfuric acid concentration be 20%；
(5) acid pickle in regulating reservoir being delivered to crystallisation by cooling tank, at a temperature of 0 DEG C, the speed with 70 revs/min continues
Stirring acid pickle, until acid pickle not recrystallization；
(6) acid pickle after crystallization is delivered to centrifugal separating device carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and
Regeneration acid solution.
Embodiment 3
The present embodiment gives up acid treatment process, containing ferrous chloride in spent acid, comprises the steps:
(1) impurity is removed through precipitation in being delivered to the acid pickle that pickling produces store up acid pond；
(2) spent acid after removing impurity is evaporated concentrating at a temperature of 55 DEG C, makes the ferrous chloride content liter in spent acid
Height, is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；
(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；
(4) copperas solution is delivered to regulating reservoir, and to add sulphuric acid to sulfuric acid concentration be 17%；
(5) acid pickle in regulating reservoir being delivered to crystallisation by cooling tank, at a temperature of 3 DEG C, the speed with 65 revs/min continues
Stirring acid pickle, until acid pickle not recrystallization；
(6) acid pickle after crystallization is delivered to centrifugal separating device carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and
Regeneration acid solution.
Following table is that give up acid treatment process and tradition of embodiment 1～3 is given up the contrast of acid treatment process:
| Traditional handicraft | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The content of regenerated acid sulphuric acid | 28% | 24% | 25% | 26% |
| The content of ferrous sulfate crystal grain | 91% | 95% | 95% | 96% |
It is about 25% that the spent acid of the present invention processes the content of sulphuric acid in the regenerated acid that PROCESS FOR TREATMENT obtains, and can meet pickling process
Requirement, i.e. regenerated acid reusable edible；The content of the ferrous sulfate crystal grain obtained is more than 95%, it is possible to reach chemical products matter
Amount standard, has the highest economic worth.
Skilled person will appreciate that of the industry, the present invention is not restricted to the described embodiments, above-described embodiment and explanation
The principle that the present invention is simply described described in book, without departing from the spirit and scope of the present invention, the present invention also has
Various changes and modifications, these changes and improvements both fall within scope of the claimed invention.Claimed scope
Defined by appending claims and equivalent thereof.
Claims (3)
1. a useless acid treatment process, containing ferrous chloride in described spent acid, it is characterised in that: comprise the steps:
(1) impurity is removed through precipitation in being delivered to the acid pickle that pickling produces store up acid pond；
(2) spent acid after removing impurity is evaporated concentrating at a temperature of 50～60 DEG C, makes the ferrous chloride in spent acid contain
Amount raises, and is dividedly in some parts excess concentrated sulphuric acid while hot, makes the chlorine in ferrous chloride replaced out；
(3) when chlorine evaporates, recovered purifying column absorb generation can reuse hydrochloric acid, generate copperas solution simultaneously；
(4) copperas solution is delivered to regulating reservoir, and to add sulphuric acid to sulfuric acid concentration be 15%～20%；
(5) acid pickle in regulating reservoir is delivered to crystallisation by cooling tank, continuously stirred acid pickle at a temperature of 0～5 DEG C, directly
To acid pickle not recrystallization；
(6) acid pickle after crystallization is delivered to centrifugal separating device carries out solid-liquid separation, respectively obtain ferrous sulfate crystal grain and
Regeneration acid solution.
Useless acid treatment process the most according to claim 1, containing ferrous chloride in described spent acid, it is characterised in that: described
In step (4) regulating reservoir, in spent acid, the concentration of sulphuric acid is 16%～18%.
Useless acid treatment process the most according to claim 1, containing ferrous chloride in described spent acid, it is characterised in that: described
The speed of step (5) stirring acid pickle is 60～70 revs/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618268.0A CN106167326A (en) | 2016-08-01 | 2016-08-01 | A kind of useless acid treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618268.0A CN106167326A (en) | 2016-08-01 | 2016-08-01 | A kind of useless acid treatment process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106167326A true CN106167326A (en) | 2016-11-30 |
Family
ID=58706122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610618268.0A Pending CN106167326A (en) | 2016-08-01 | 2016-08-01 | A kind of useless acid treatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106167326A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043092A (en) * | 2017-04-05 | 2017-08-15 | 珠海绿水环保科技有限公司 | A kind of energy-saving metallurgical recovery treatment method of waste acid and device |
| CN107117992A (en) * | 2017-06-12 | 2017-09-01 | 贵州诺威施生物工程有限公司 | Calcium chloride preparation system and calcium chloride preparation method |
| CN118495482A (en) * | 2024-07-15 | 2024-08-16 | 南通山剑防腐科技有限公司 | Stainless steel waste acid treatment process |
| CN119551841A (en) * | 2024-11-13 | 2025-03-04 | 无锡天控工业技术有限公司 | An automated treatment system for metal pickling waste acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369574A (en) * | 2001-02-12 | 2002-09-18 | 朝宁工程顾问股份有限公司 | Manufacturing method and device for extracting useful substances from waste acid |
| CN102784491A (en) * | 2012-08-28 | 2012-11-21 | 重庆钢铁(集团)有限责任公司 | Waste acid treatment process |
| CN105776139A (en) * | 2016-03-16 | 2016-07-20 | 江苏双能太阳能有限公司 | Waste acid treatment process |
-
2016
- 2016-08-01 CN CN201610618268.0A patent/CN106167326A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369574A (en) * | 2001-02-12 | 2002-09-18 | 朝宁工程顾问股份有限公司 | Manufacturing method and device for extracting useful substances from waste acid |
| CN102784491A (en) * | 2012-08-28 | 2012-11-21 | 重庆钢铁(集团)有限责任公司 | Waste acid treatment process |
| CN105776139A (en) * | 2016-03-16 | 2016-07-20 | 江苏双能太阳能有限公司 | Waste acid treatment process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043092A (en) * | 2017-04-05 | 2017-08-15 | 珠海绿水环保科技有限公司 | A kind of energy-saving metallurgical recovery treatment method of waste acid and device |
| CN107117992A (en) * | 2017-06-12 | 2017-09-01 | 贵州诺威施生物工程有限公司 | Calcium chloride preparation system and calcium chloride preparation method |
| CN118495482A (en) * | 2024-07-15 | 2024-08-16 | 南通山剑防腐科技有限公司 | Stainless steel waste acid treatment process |
| CN119551841A (en) * | 2024-11-13 | 2025-03-04 | 无锡天控工业技术有限公司 | An automated treatment system for metal pickling waste acid |
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| PB01 | Publication | ||
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Application publication date: 20161130 |