CN106167326A - A kind of useless acid treatment process - Google Patents

A kind of useless acid treatment process Download PDF

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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
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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
Application number
CN201610618268.0A
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Chinese (zh)
Inventor
钱园
郭启林
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JIANGSU SUNRISE CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
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JIANGSU SUNRISE CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
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Application filed by JIANGSU SUNRISE CHEMICAL ENGINEERING TECHNOLOGY Co Ltd filed Critical JIANGSU SUNRISE CHEMICAL ENGINEERING TECHNOLOGY Co Ltd
Priority to CN201610618268.0A priority Critical patent/CN106167326A/en
Publication of CN106167326A publication Critical patent/CN106167326A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities

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  • 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

A kind of useless acid treatment process
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.
CN201610618268.0A 2016-08-01 2016-08-01 A kind of useless acid treatment process Pending CN106167326A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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

Citations (3)

* Cited by examiner, † Cited by third party
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 Process and equipment for extracting useful substances from use 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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 Process and equipment for extracting useful substances from use 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 (2)

* Cited by examiner, † Cited by third party
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

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Application publication date: 20161130