CN108101121A - A kind of resource recycling method of iron content waste sulfuric acid solution - Google Patents

A kind of resource recycling method of iron content waste sulfuric acid solution Download PDF

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Publication number
CN108101121A
CN108101121A CN201711384850.6A CN201711384850A CN108101121A CN 108101121 A CN108101121 A CN 108101121A CN 201711384850 A CN201711384850 A CN 201711384850A CN 108101121 A CN108101121 A CN 108101121A
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China
Prior art keywords
sulfuric acid
iron
iron content
acid solution
content waste
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CN201711384850.6A
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Chinese (zh)
Inventor
陈青松
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Thumb Environmental Protection Equipment (tianjin) Co Ltd
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Thumb Environmental Protection Equipment (tianjin) Co Ltd
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Priority to CN201711384850.6A priority Critical patent/CN108101121A/en
Publication of CN108101121A publication Critical patent/CN108101121A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/90Separation; Purification
    • C01B17/901Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/14Sulfates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

The invention discloses a kind of resource recycling methods of iron content waste sulfuric acid solution, comprise the following steps:Iron content waste sulfuric acid solution is added in pretreatment reaction kettle, iron powder is added in pretreatment reaction kettle and heavy metal chelating agent carries out mixing reaction, filters, obtains reaction solution;Reaction solution is promoted in crystallization reactor, cooling while adds in industrial sulphuric acid in crystallization reactor by a certain percentage to be mixed, reactive crystallization, and filtering obtains two kinds of products:High-purity sulfuric acid ferrous iron crystal (solid) and dilution heat of sulfuric acid.The beneficial effects of the invention are as follows:Two kinds of products are obtained from iron content sulfuric acid solution:High-purity sulfuric acid ferrous iron crystal (solid) and dilution heat of sulfuric acid, technological operation is simple, production safety is environmentally friendly, sulfuric acid utilization rate is high, without discharging of waste liquid, good in economic efficiency.The ferrous sulfate of acquisition, storage and transport are convenient, content of beary metal is extremely low, added value is high, for molysite processed, iron oxide pigment, mordant, water purification agent, corrosion-proof and sterilization agent etc..

Description

A kind of resource recycling method of iron content waste sulfuric acid solution
Technical field:
The invention belongs to dangerous waste disposal, resource regeneration and technical fields of developing a circular economy, and are related to a kind of utilize and contain Iron waste sulfuric acid solution prepares high-purity sulfuric acid ferrous iron crystal and the method for recycling dilution heat of sulfuric acid.
Background technology:
With the rapid development of the national economy, in ferrous metal product acid cleaning process, substantial amounts of iron content waste sulfuric acid solution is carried secretly It generates, the sulfuric acid containing different quality containing and substantial amounts of Fe in waste liquid2+, secondly it is Fe3+、Cu2+、Cr6+、Mg2+、Si4+、Pb2+、 Ni2+Etc. heavy metal ion presence.How efficiently, rationally processing iron content waste sulfuric acid solution is in an emphasis of efforts at environmental protection Hold.In the case where realizing resource regeneration and the policy developed a circular economy guide, the resource in iron content waste sulfuric acid solution is realized regeneration It recycles and recycles, so as to generate huge environmental benefit and economic benefit.(one kind contains high-concentration sulfuric acid to CN105152229A Ferrous Waste Sulfuric Acid purification-recovery system and recovery process) it is by the Waste Sulfuric Acid of the ferrous iron containing high-concentration sulfuric acid, directly freezed crystallizes, After centrifugation, product is obtained as ferrous sulfate heptahydrate crystal product.After liquid after centrifugation is using heating, pass through film Piece-rate system filters, and the dope after filtering is mixed into waste sulfuric acid solution circular treatment, and the clear liquid after filtering recycles for dilution heat of sulfuric acid. The method does not pre-process the heavy metal in waste sulfuric acid solution and suspended matter, the heavy metal in ferrous sulfate heptahydrate crystal and Suspension content is high, and the product quality of ferrous sulfate heptahydrate is unqualified, it is impossible to smoothly be back to industrial production.Using membrane filtration system System needs to carry out high-pressure filteration to liquid, and also needs to heat raising fluid temperature again, and equipment investment and operation energy consumption are higher.Film Filtration system also needs periodically to backwash, and high failure rate adds degree complicated for operation.
The present invention seeks to iron content waste sulfuric acid solution is prepared high-purity sulfuric acid ferrous iron crystal (solid) by certain condition And dilution heat of sulfuric acid is recycled, heavy metal and suspended matter in iron content waste sulfuric acid solution are effectively removed, it is ferrous to expand high-purity sulfuric acid The application range of crystal realizes dilute sulfuric acid circulating and recovering nearby, reduces equipment investment and operation energy consumption, increase economic efficiency.It should Research can not only solve the problem of environmental pollution caused by spent acid discharges, but also achieve the purpose that resource recycling.
The content of the invention:
The technical problem to be solved by the present invention is to:Based on the above problem, the present invention provides a kind of iron content waste sulfuric acid solution Resource recycling method can obtain two kinds of products:High-purity sulfuric acid ferrous iron crystal (solid) and dilution heat of sulfuric acid.
A technical solution is used by the present invention solves its technical problem:A kind of resource of iron content waste sulfuric acid solution is returned Application way is received, is comprised the following steps:
The preparation of reaction solution:By iron content waste sulfuric acid solution add in pretreatment reaction kettle, stirring, add in heavy metal chelating agent and Iron powder, after reaction, by obtaining reaction solution after filtering.
It is prepared by high-purity sulfuric acid ferrous iron crystal and dilution heat of sulfuric acid:Reaction solution is promoted to crystallization reactor, cools down, stirs It mixes, industrial sulphuric acid is added in, after reacting and crystallizing, by the way that two kinds of products are obtained by filtration:High-purity sulfuric acid ferrous iron crystal (solid) and Dilution heat of sulfuric acid.
Further, the heavy metal chelating agent in step (1) is fluid chemical medicament, can carry out strong chela with heavy metal ion It closes and reacts and formed flocky precipitate.The dosage of heavy metal chelating agent is iron content Waste Sulfuric Acid 0.01%~0.5%.
Further, the grain size of the iron powder in step (1) is the mesh of 100 mesh~300, active Fe content >=98%.
Further, the reaction temperature in step (1) is controlled between 5~45 DEG C.
Further, the mass percent of the industrial sulphuric acid in step (2) is 80%~98%, and dosage is iron content sulfur waste The mass percent of acid solution is 1%~20%.
Further, the reaction temperature in step (2) is controlled between -25~45 DEG C.
Further, heavy metal mass percentage is less than 0.001% in high-purity sulfuric acid ferrous iron crystal in step (2).
Further, the mass percentage of sulfuric acid is 10%~40% in dilution heat of sulfuric acid in step (2), weight of iron Percentage composition is calculated as 0.1%~10% with ferrous sulfate.
The beneficial effects of the invention are as follows:
Two kinds of products are obtained from iron content sulfuric acid solution:High-purity sulfuric acid ferrous iron crystal (solid) and dilution heat of sulfuric acid, Technological operation is simple, production safety is environmentally friendly, sulfuric acid utilization rate is high, without discharging of waste liquid, good in economic efficiency.The high-purity sulfuric acid of acquisition Ferrous crystal is solid, and storage and transport are convenient, content of beary metal is extremely low in product, added value is high, available for molysite processed, oxidation Iron pigment, mordant, water purification agent, preservative, disinfectant etc.;The dilution heat of sulfuric acid of acquisition, content of beary metal is low, insolubles content It is extremely low, ferrous metal product spent pickling acid, no discharging of waste liquid can be recycled to be used on the spot, and liquid long-distance transport inconvenience is avoided, Improve the utilization rate of sulfuric acid.The present invention realizes the resource regeneration of iron content waste sulfuric acid solution and all recycles, maximum limit Degree improves the utilization rate of sulfuric acid, realizes the zero-emission of iron content sulfuric acid solution in ferrous metal product acid cleaning process, can obtain pole Big environment benefits and economic gains.
Specific embodiment:
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than Limitation of the invention further.
Embodiment 1
1000kg iron content waste sulfuric acid solution (ferrous sulfate content 25%, sulfuric acid content are added into pretreatment reaction kettle 10%), start to stir, then add 0.1kg iron powders, after reacting half an hour, add 1kg heavy metal chelating agents, then to react half small Shi Hou is separated by filtration by filter, obtains reaction solution.Control more than reaction temperature is between 5~45 DEG C.
Reaction solution is promoted to crystallization reactor, starts to stir, opens refrigeration system controlling reaction temperature, control is above anti- Temperature is answered between -25~45 DEG C.The industrial sulphuric acid that 110kg mass fractions are 98% is added into reaction kettle, starts to stir, instead Should and crystallize 2.5 it is small when after, by the way that two kinds of products are obtained by filtration:High-purity sulfuric acid ferrous iron crystal (solid) and dilution heat of sulfuric acid. Mass fraction >=85% of ferrous sulfate heptahydrate in high-purity sulfuric acid ferrous iron crystal, lead (Pb)≤0.001%, arsenic (As)≤ 0.001%, water-insoluble≤0.10%;Sulfuric acid mass fraction >=20% of dilution heat of sulfuric acid, iron content in terms of ferrous sulfate≤ 5%, content of beary metal≤0.001%.
Embodiment 2
200kg/h iron content waste sulfuric acid solution is continuously added into pretreatment reaction kettle, and (ferrous sulfate content 25%, sulfuric acid contains 10%) amount, continuously stirs, then continuously adds the iron powder of 0.02kg/h, continuously add the heavy metal chelating agent of 0.2kg/h, even It is continuous to be separated by filtration by filter, obtain reaction solution.Control more than reaction temperature is between 5~45 DEG C.
It by reaction solution continuance lifting to crystallization reactor, continuously stirs, refrigeration system controlling reaction temperature is at -25~45 DEG C Between.Continuously added into reaction kettle 21kg/h mass fractions be 98% industrial sulphuric acid, react and crystallize 2.5 it is small when after, will The mixed liquor of sulfur acid ferrous iron crystal, which continues through, is obtained by filtration two kinds of products:High-purity sulfuric acid ferrous iron crystal (solid) and dilute sulphur Acid solution.Mass fraction >=85% of the ferrous sulfate heptahydrate of high-purity sulfuric acid ferrous iron crystal, lead (Pb)≤0.001%, arsenic (As)≤0.001%, water-insoluble≤0.10%;Sulfuric acid mass fraction >=20% of dilution heat of sulfuric acid, iron content are sub- with sulfuric acid Iron meter≤7%, content of beary metal≤0.001%.
Using above-mentioned desirable embodiment according to the invention as enlightenment, by above-mentioned description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property scope is not limited to the content on specification, it is necessary to determine its technical scope according to right.

Claims (9)

1. a kind of resource recycling method of iron content waste sulfuric acid solution, it is characterized in that comprising the following steps:
(1) preparation of reaction solution:By iron content waste sulfuric acid solution add in pretreatment reaction kettle, stirring, add in heavy metal chelating agent and Iron powder, after reaction, by obtaining reaction solution after filtering;
(2) prepared by high-purity sulfuric acid ferrous iron crystal and dilution heat of sulfuric acid:Reaction solution is promoted to crystallization reactor, is cooled down, stirring, Industrial sulphuric acid is added in, after reacting and crystallizing, by the way that two kinds of products are obtained by filtration:The high-purity sulfuric acid ferrous iron crystal and dilute sulphur of solid Acid solution.
2. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (1) in iron content Waste Sulfuric Acid, be the sulfuric acid waste periodically discharged in ferrous metal product acid cleaning process, weight of iron percentage contains Amount is calculated as 1%~30% with ferrous sulfate, and sulfuric acid mass percentage is 5%~30%.
3. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (1) in heavy metal chelating agent for fluid chemical medicament, strong chelatropic reaction can be carried out with heavy metal ion and forms wadding Shape sediment.The dosage of heavy metal chelating agent is that iron content Waste Sulfuric Acid mass percentage is 0.01%~0.5%.
4. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (1) in the grain size of iron powder be the mesh of 100 mesh~300, active iron mass percentage >=98%.
5. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (1) in reaction temperature control between 5~45 DEG C.
6. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (2) in industrial sulphuric acid mass percentage for 80%~98%, dosage is the quality of iron content waste sulfuric acid solution Percentage composition is 1%~20%.
7. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (2) in reaction temperature control between -25~45 DEG C.
8. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (2) in high-purity sulfuric acid ferrous iron crystal heavy metal mass percentage be less than 0.001%.
9. a kind of resource recycling method of iron content waste sulfuric acid solution according to claim 1, it is characterised in that:It is described The step of (2) in dilution heat of sulfuric acid the mass percentage of sulfuric acid be 10%~40%, weight of iron percentage composition is with sulfuric acid Ferrous iron is calculated as 0.1%~10%.
CN201711384850.6A 2017-12-20 2017-12-20 A kind of resource recycling method of iron content waste sulfuric acid solution Pending CN108101121A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074284A (en) * 2020-01-03 2020-04-28 华东理工大学 Safe pollution-free emission steel pickling process and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102139927A (en) * 2011-01-17 2011-08-03 升华集团德清华源颜料有限公司 High-purity iron oxide black pigment and production method thereof
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102139927A (en) * 2011-01-17 2011-08-03 升华集团德清华源颜料有限公司 High-purity iron oxide black pigment and production method thereof
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074284A (en) * 2020-01-03 2020-04-28 华东理工大学 Safe pollution-free emission steel pickling process and application thereof

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