CN104498974B - A kind of method that mixed acid is reclaimed in the pickle liquor from cold-rolling stainless steel - Google Patents
A kind of method that mixed acid is reclaimed in the pickle liquor from cold-rolling stainless steel Download PDFInfo
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- CN104498974B CN104498974B CN201510037110.XA CN201510037110A CN104498974B CN 104498974 B CN104498974 B CN 104498974B CN 201510037110 A CN201510037110 A CN 201510037110A CN 104498974 B CN104498974 B CN 104498974B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Abstract
A kind of method the present invention relates to reclaim the mixed acid containing nitric acid Yu hydrofluoric acid in pickle liquor from cold-rolling stainless steel, the method includes the steps such as concentration, displacement are reacted, separate, condensation is reclaimed.The present invention overcomes existing cold-rolling stainless steel pickle liquor Treatment process defect, cold-rolling stainless steel pickle liquor is realized thoroughly to administer, there is no runoff water to discharge, non-secondary pollution, waste acidity recovery regeneration, resources circulation is realized to recycle, therefore, fully comply with typical green economy concept, be it is a kind of benefit the nation, excellent process favorable to the people, beneficial to pollution treatment enterprise development.
Description
【Technical field】
The invention belongs to industrial waste acid processing technology field.More particularly it relates to one kind is sour from cold-rolling stainless steel
The method for reclaiming the mixed acid containing nitric acid Yu hydrofluoric acid is washed in waste liquid.
【Background technology】
Stainless-steel cold-rolling method includes the step of removing oxide through pickling, and the acid for using is the mixing of nitric acid and hydrofluoric acid
Acid.Therefore, stainless steel acid-washing waste liquid usually contains ferric nitrate, nitric acid, hydrofluoric acid etc..Prior art is usually using 8-18% nitric acid
With the mixed acid of 8-10% hydrofluoric acid, after through multiple pickling, the metal ion in the pickle liquor increases to certain dense
(such as when iron content reaches about 40 g/l), described mixed acid loses pickling ability and turns into spent acid degree.Now in acid pickle
Total acidity be typically about 8%, and contain substantial amounts of iron, nickel, chromic salts.
Existing pickle liquor " innoxious " processing method is to close the cleaning waste water that useless mixed acid and acid cleaning process are produced
And, by alkaline cleaning, make composite waste pH qualified discharges, and for heavy metal (F in its waste residue-, Cr+6、Cr+3、Fe+2、Fe+3、Ni+1) etc. pollutant then professional institution must be specified separately to deal with by environmental administration, the result is that spent acid is not only without can
It is effectively addressed, but also wastes ample resources, it is often more important that alkaline cleaning is inevitable with a large amount of wastes (solid)
Produce secondary pollution.
A kind of more ripe pickle liquor handling process is spray roasting technique.The technique is reclaimed using high-temperature decomposition
HF、HNO3Acid and stainless steel metal oxidate powder (or ball), spray roasting technique have that environmental protection effect is good, economic well-being of workers and staff valency
The characteristics of being worth high.Its regenerative mixed acid reclaimed can be recycled, and metal oxide can be made for stainless steel powder metallurgical or steel-making
Raw material, but, because its processing cost is high and can only be difficult to popularize by import equipment.
Another pickle liquor handling process is ion-exchange process in the prior art.The technology utilization ion exchange resin
(or amberplex) selection absorbs (or infiltration) principle, free state HF, HNO in waste acid recovery3.Ion-exchange process is because only
Free acid in waste acid recovery, and regeneration acid concentration is less than free acid concentration, total acid recovering rate≤45% in spent acid.Also wait body
The mixing hydrochlorate raffinate discharge of accumulated amount need to carry out environmental protection treatment, and cost for wastewater treatment then greatly improved.Therefore, macroeconomy
Value is low, such as also there are problems that cooling and explosion-proof technology using resin method, so equally existing defect.
Therefore, the present inventor, by lot of experiments and analysis, completes finally on the basis of prior art is summarized
The present invention.
【The content of the invention】
[technical problem to be solved]
It is mixed with hydrofluoric acid containing nitric acid it is an object of the invention to provide being reclaimed in a kind of pickle liquor from cold-rolling stainless steel
The method for closing acid.
[technical scheme]
The present invention is achieved through the following technical solutions.
A kind of side the present invention relates to reclaim the mixed acid containing nitric acid Yu hydrofluoric acid in pickle liquor from cold-rolling stainless steel
Method.The step of methods described, is as follows：
A, concentration
Described cold-rolling stainless steel pickle liquor is allowed to be concentrated under conditions of 110~150 DEG C of temperature, until the acid
Wash waste liquid and reach NO3 -Content for by weight 4%~6%, Fe ion concentrations for by weight 1.56%~
41.0%, pH value≤2 obtain a kind of oversaturated concentrating waste acid of nitrate, and one kind contains 4~6% nitric acid by weight
With the diluted acid condensate liquid of 2~3% hydrofluoric acid；
B, displacement reaction
Add the concentrated sulfuric acid in the nitrate supersaturation concentrating waste acid obtained toward step A, the nitrate supersaturation spent acid with
The weight ratio of the concentrated sulfuric acid is 1:0.2~0.6, it is well mixed, then in the bar of 100~130 DEG C of temperature and 0.1~0.3MPa of pressure
Reacted 0.5~8.5 hour under part,
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to enter under conditions of -25 DEG C~25 DEG C of temperature with pressure 0.004-0.06MPa
Row crystallisation by cooling, obtains containing 45%~55% ferrous sulfate hydrate in mass through separation of solid and liquid, at the same obtain concentration be with
The sulphate of iron raffinate of quality meter 5%~15%；
D condensations are reclaimed
The gas containing hydrogen fluoride and nitric acid that step B is obtained is allowed to be inhaled in gas with the diluted acid condensate liquid obtained in step A
Contacted in receiving unit, hydrogen fluoride and nitric acid are absorbed under conditions of 40~60 DEG C of temperature with pressure 0.04-0.06MPa, obtain institute
The mixed acid containing hydrogen fluoride and nitric acid stated.
Another preferred embodiment of the invention, in step, described nitrate supersaturation spent acid contain with
Weight meter other metal ions below 0.40% and nonmetallic ion and 2%~3% hydrofluoric acid.
A preferred embodiment of the invention, in step, the concentration systems for using are assemblings by polytetrafluoroethyl-ne
The conventional triple effect evaporation system of the evaporation equipment that alkene impregnated graphite is made.
Another preferred embodiment of the invention, in stepb, the equipment for replacing reaction is that a kind of using is gathered
The popular response kettle that tetrafluoroethene impregnated graphite is made.
Another preferred embodiment of the invention, in step C, described sulphate of iron raffinate first uses normal-temperature water
Cooling, is then water-cooled to temperature -15~25 DEG C, then separation of solid and liquid with freezing, obtains the solid containing sulfate with dilute sulphur
Acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement reaction in step B.
Another preferred embodiment of the invention, in step D, described gas absorption equipment is to use polytetrafluoro
The conventional gas absorption equipment that ethene impregnated graphite is made.
Another preferred embodiment of the invention, in step D, it be in mass 14- that the mixed acid contains
17% nitric acid and 5-7% hydrofluoric acid.
Another preferred embodiment of the invention, described polytetrafluoroethylimpregnated impregnated graphite is by the following method
Prepare：
Graphite is placed in concentration in 58%~75% polytetrafluoroethyldispersion dispersion by weight, then pressure 0.3~
Impregnated 6~12 hours under conditions of 0.9MPa, 14- is sintered under conditions of 360-400 DEG C of temperature in the sintering furnace again after drying
18 hours, obtain described polytetrafluoroethylimpregnated impregnated graphite.
The present invention is described in more detail below.
A kind of side the present invention relates to reclaim the mixed acid containing nitric acid Yu hydrofluoric acid in pickle liquor from cold-rolling stainless steel
Method.The step of methods described, is as follows：
A, concentration
Described cold-rolling stainless steel pickle liquor is allowed to be concentrated under conditions of 110~150 DEG C of temperature, until the acid
Wash waste liquid and reach NO3 -Content for by weight 4%~6%, Fe ion concentrations be by weight 1.56%~41.0%, pH value≤
2, a kind of oversaturated concentrating waste acid of nitrate is obtained, and one kind contains 4~6% nitric acid and 2~3% hydrofluoric acid by weight
Diluted acid condensate liquid；
In this step, the concentration systems that described cold-rolling stainless steel pickle liquor is used when concentrating are assemblings by poly- four
The conventional triple effect evaporation system of the evaporation equipment that PVF impregnated graphite is made.
Conventional triple effect evaporation system is widely used device in current chemical technology field.The routine three that the present invention is used
Effect vapo(u)rization system is the vaporising device sold in the market, and wherein evaporation equipment part is by polytetrafluoroethylimpregnated impregnated graphite system
Into.
In this step, determined using conventional chemical analysis method, the NO in the pickle liquor3 -Content and Fe ions
It is other metal ions and nonmetallic ion content and fluohydric acid content in content, nitrate supersaturation spent acid, described dilute
Nitric acid and fluohydric acid content in acid condensation liquid.
Described polytetrafluoroethylimpregnated impregnated graphite is prepared by the following method：
Graphite is placed in concentration in 58%~75% polytetrafluoroethyldispersion dispersion by weight, then pressure 0.3~
Impregnated 6~12 hours under conditions of 0.9MPa, 14- is sintered under conditions of 360-400 DEG C of temperature in the sintering furnace again after drying
18 hours, obtain described polytetrafluoroethylimpregnated impregnated graphite.
The polytetrafluoroethyldispersion dispersion that the present invention is used is the product sold in the market.
The drying equipment and sintering furnace that the present invention is used all are widely used devices in current chemical technology field, are all
The product sold in the market.
B, displacement reaction
Add the concentrated sulfuric acid in the nitrate supersaturation concentrating waste acid obtained toward step A, the nitrate supersaturation spent acid with
The weight ratio of the concentrated sulfuric acid is 1:0.2~0.6, it is well mixed, then in the bar of 100~130 DEG C of temperature and 0.1~0.3MPa of pressure
Reacted 0.5~8.5 hour under part；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
In this step, it is that a kind of routine being made of polytetrafluoroethylimpregnated impregnated graphite is anti-for replacing the equipment of reaction
Answer kettle.The popular response kettle structure that the present invention is used all is reactor structure widely used in current chemical technology field, only
It is made of it with polytetrafluoroethylimpregnated impregnated graphite.Polytetrafluoroethylimpregnated impregnated graphite will not be repeated here previously mentioned.
Described crystallization is to allow reactant mixture to stand at room temperature, allows sulfate spontaneous nucleation, is separated out from its mother liquor,
Separate the mixing acid pickle that the mother liquor obtained after crystal is containing sulfate.
Described separation is separated with equipment from conventional separation methods in chemical technology field, these separation equipments
It is widely used device in current chemical technology field, is also all the product sold in the market.
The sulfate solid that the step is obtained can for example be used in water treatment technology as water purification agent commodity.
C, separation
The mixing acid pickle that step B is obtained is allowed to enter under conditions of -25 DEG C~25 DEG C of temperature with pressure 0.004-0.06MPa
Row crystallisation by cooling, obtains containing 45%~55% ferrous sulfate hydrate in mass through separation of solid and liquid, at the same obtain concentration be with
The sulphate of iron raffinate of quality meter 5%~15%；
The equipment that the step crystallisation by cooling is used is widely used cooling crystallizing equipment in current chemical technology field,
Also all it is the product sold in the market.
In this step, described sulphate of iron raffinate first uses normal temperature water cooling, then with freezing be water-cooled to temperature-
15~25 DEG C, then separation of solid and liquid, obtains the solid containing sulfate and dilute sulfuric acid mother liquor, and described dilute sulfuric acid mother liquor is returned again to
Displacement reaction is participated in in step B.
Solid-liquid separating method is as previously described with equipment.
D condensations are reclaimed
The gas containing hydrogen fluoride and nitric acid that step B is obtained is allowed to be inhaled in gas with the diluted acid condensate liquid obtained in step A
Contacted in receiving unit, hydrogen fluoride and nitric acid are absorbed under conditions of 40~60 DEG C of temperature with pressure 0.04-0.06MPa, obtain institute
The mixed acid containing hydrogen fluoride and nitric acid stated.
In this step, described gas absorption equipment is widely used conventional gas in current chemical technology field
Absorption equipment, it is the conventional gas absorption equipment being made of polytetrafluoroethylimpregnated impregnated graphite.Polytetrafluoroethylimpregnated impregnated graphite is
Previously mentioned, will not be repeated here.
Determined using conventional chemical analysis method, it be in mass 14-17% nitric acid and 5-7% hydrogen that the mixed acid contains
Fluoric acid.
[beneficial effect]
The beneficial effects of the invention are as follows：Compared with prior art, the present invention overcomes existing cold-rolling stainless steel pickling
Treating waste liquid technological deficiency, realizes cold-rolling stainless steel pickle liquor and thoroughly administers, and does not have runoff water to discharge, without secondary dirt
Dye, realizes waste acidity recovery regeneration, resources circulation and recycles, therefore, fully comply with typical green economy concept.
There is the inventive method environmental protection, resource regeneration, pollution treatment also to get a profit (relatively existing handling process) effect, because
This, the method for the present invention be it is a kind of benefit the nation, excellent process favorable to the people, beneficial to pollution treatment enterprise development.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 140 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 4.6%, Fe ion concentrations are by weight 29.1%, and pH value≤2 obtain a kind of oversaturated thickened waste of nitrate
Acid, it contains less than 0.40% other metal ions by weight and nonmetallic ion and 2.8% hydrofluoric acid, also obtains one kind
Diluted acid condensate liquid containing 4.0% nitric acid by weight and 3.0 hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.2, it is well mixed, then in temperature
Reacted 6.2 hours under conditions of 100 DEG C and pressure 0.1MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to carry out crystallisation by cooling under conditions of -25 DEG C of temperature with pressure 0.01MPa,
Obtained containing 48% ferrous sulfate hydrate in mass through separation of solid and liquid, while obtaining the ferric sulfate that concentration is in mass 5%
Salt raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to -15 DEG C of temperature with freezing, then solid-liquid
Separate, obtain the solid containing sulfate and dilute sulfuric acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement in step B
Reaction.
D condensations are reclaimed
The gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A are allowed with poly- four
Contacted in the gas absorption equipment that PVF impregnated graphite is made, fluorine is absorbed under conditions of 40 DEG C of temperature with pressure 0.04MPa
Change hydrogen and nitric acid, obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and the mixed acid contains with quality
It is calculated as 17.0% nitric acid and 5.0% hydrofluoric acid.
The polytetrafluoroethylimpregnated impregnated graphite that the present embodiment is used is prepared by the following method：
It is by weight in the dispersion liquid of 55% polytetrafluoroethylene (PTFE), then in the bar of pressure 0.9MPa that graphite is placed in into concentration
Impregnated 6 hours under part, sintered 18 hours under conditions of 360 DEG C of temperature in the sintering furnace again after drying, obtain described poly- four
PVF impregnated graphite.
Embodiment 2：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 110 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 4.0%, Fe ion concentrations are by weight 37.2%, and pH value≤2 obtain a kind of oversaturated thickened waste of nitrate
Acid, it contains less than 0.40% other metal ions by weight and nonmetallic ion and 2.0% hydrofluoric acid, also obtains one kind
Diluted acid condensate liquid containing 6.0% nitric acid by weight and 2.4% hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.4, it is well mixed, then in temperature
Reacted 0.5 hour under conditions of 130 DEG C and pressure 0.2MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to carry out crystallisation by cooling under conditions of -10 DEG C of temperature with pressure 0.004MPa,
Obtained containing 52% ferrous sulfate hydrate in mass through separation of solid and liquid, while obtaining the ferric sulfate that concentration is in mass 15%
Salt raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to 0 DEG C of temperature with freezing, then solid-liquid point
From, the solid containing sulfate and dilute sulfuric acid mother liquor are obtained, described dilute sulfuric acid mother liquor again returns to participate in displacement instead in step B
Should.
D condensations are reclaimed
Allow the gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A with implementation
Contacted in the identical gas absorption equipment of example 1, hydrogen fluoride and nitric acid absorbed under conditions of 46 DEG C of temperature with pressure 0.05MPa,
Obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and it be in mass 14.% nitre that the mixed acid contains
Acid and 6.8% hydrofluoric acid.
Embodiment 3：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 125 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 5.4%, Fe ion concentrations are by weight 1.56%, and pH value≤2 obtain a kind of oversaturated thickened waste of nitrate
Acid, it contains less than 0.40% other metal ions by weight and nonmetallic ion and 2.5% hydrofluoric acid, also obtains one kind
Diluted acid condensate liquid containing 4.5% nitric acid by weight and 2.0% hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.5, it is well mixed, then in temperature
Reacted 4.0 hours under conditions of 110 DEG C and pressure 0.3MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
Allow the mixing acid pickle that step B is obtained to carry out crystallisation by cooling under conditions of 25 DEG C of temperature with pressure 0.06MPa, pass through
Separation of solid and liquid is obtained containing 55% ferrous sulfate hydrate in mass, while obtaining the sulphate of iron that concentration is in mass 8%
Raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to 10 DEG C of temperature with freezing, then solid-liquid
Separate, obtain the solid containing sulfate and dilute sulfuric acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement in step B
Reaction.
D condensations are reclaimed
Allow the gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A with implementation
Contacted in the identical gas absorption equipment of example 1, hydrogen fluoride and nitric acid absorbed under conditions of 53 DEG C of temperature with pressure 0.06MPa,
Obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and it be in mass 15.2% that the mixed acid contains
Nitric acid and 7.0% hydrofluoric acid.
Embodiment 4：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 150 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 6.0%, Fe ion concentrations are by weight 16.2%, and pH value≤2 obtain a kind of oversaturated thickened waste of nitrate
Acid, it contains less than 0.40% other metal ions by weight and nonmetallic ion and 3.0% hydrofluoric acid, also obtains one kind
Diluted acid condensate liquid containing 5.6% nitric acid by weight and 2.6% hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.6, it is well mixed, then in temperature
Reacted 8.5 hours under conditions of 120 DEG C and pressure 0.2MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
Allow the mixing acid pickle that step B is obtained to carry out crystallisation by cooling under conditions of 10 DEG C of temperature with pressure 0.03MPa, pass through
Separation of solid and liquid is obtained containing 45% ferrous sulfate hydrate in mass, while obtaining the sulphate of iron that concentration is in mass 12%
Raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to 25 DEG C of temperature with freezing, then solid-liquid
Separate, obtain the solid containing sulfate and dilute sulfuric acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement in step B
Reaction.
D condensations are reclaimed
The gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A are allowed with poly- four
Contacted in the gas absorption equipment that PVF impregnated graphite is made, fluorine is absorbed under conditions of temperature 60 C and pressure 0.05MPa
Change hydrogen and nitric acid, obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and the mixed acid contains with quality
It is calculated as 16.4% nitric acid and 5.2% hydrofluoric acid.
The polytetrafluoroethylimpregnated impregnated graphite that the present embodiment is used is prepared by the following method：
It is by weight in the dispersion liquid of 60% polytetrafluoroethylene (PTFE), then in the bar of pressure 0.3MPa that graphite is placed in into concentration
Impregnated 12 hours under part, sintered 14 hours under conditions of 400 DEG C of temperature in the sintering furnace again after drying, obtain described poly- four
PVF impregnated graphite.
Embodiment 5：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 130 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 4.3%, Fe ion concentrations are by weight 5.0%, and pH value≤2 obtain a kind of oversaturated concentrating waste acid of nitrate,
It contains less than 0.40% other metal ions by weight and nonmetallic ion and 2.4% hydrofluoric acid, also obtains one kind and contains
There is the diluted acid condensate liquid of 5.0% nitric acid by weight and 2.7% hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.3, it is well mixed, then in temperature
Reacted 3.3 hours under conditions of 115 DEG C and pressure 0.15MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to carry out cooling knot under conditions of -12.5 DEG C of temperature with pressure 0.025MPa
Crystalline substance, obtains containing 50% ferrous sulfate hydrate in mass through separation of solid and liquid, while it is with the sulfuric acid of quality 10% to obtain concentration
Molysite raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to -8 DEG C of temperature with freezing, then solid-liquid
Separate, obtain the solid containing sulfate and dilute sulfuric acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement in step B
Reaction.
D condensations are reclaimed
Allow the gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A with implementation
Contacted in the identical gas absorption equipment of example 4, hydrogen fluoride and nitric acid absorbed under conditions of 43 DEG C of temperature with pressure 0.045MPa,
Obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and it be in mass 15.8% that the mixed acid contains
Nitric acid and 6.3% hydrofluoric acid.
Embodiment 6：The present invention reclaims mixed acid from cold-rolling stainless steel pickle liquor
The implementation steps of the embodiment are as follows：
A, concentration
Using a kind of triple effect evaporation system of evaporation equipment assembled and be made up of polytetrafluoroethylimpregnated impregnated graphite, allow described
Cold-rolling stainless steel pickle liquor is concentrated under conditions of 135 DEG C of temperature, until the pickle liquor reaches NO3 -Content be with
Weight meter 5.7%, Fe ion concentrations are by weight 41.0%, and pH value≤2 obtain a kind of oversaturated thickened waste of nitrate
Acid, it contains less than 0.40% other metal ions by weight and nonmetallic ion and 2.8% hydrofluoric acid, also obtains one kind
Diluted acid condensate liquid containing 5.1% nitric acid by weight and 2.3% hydrofluoric acid；
B, displacement reaction
In the reactor being made of polytetrafluoroethylimpregnated impregnated graphite, toward the nitrate supersaturation thickened waste that step A is obtained
The concentrated sulfuric acid is added in acid, the nitrate supersaturation spent acid and the weight ratio of the concentrated sulfuric acid are 1:0.56, it is well mixed, then in temperature
Reacted 6.5 hours under conditions of 115 DEG C and pressure 0.25MPa of degree；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is entered
Row crystallization, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to carry out crystallisation by cooling under conditions of 18 DEG C of temperature with pressure 0.045MPa,
Obtained containing 49% ferrous sulfate hydrate in mass through separation of solid and liquid, while obtaining the ferric sulfate that concentration is in mass 11%
Salt raffinate；
Described sulphate of iron raffinate first uses normal temperature water cooling, is then water-cooled to 18 DEG C of temperature with freezing, then solid-liquid
Separate, obtain the solid containing sulfate and dilute sulfuric acid mother liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement in step B
Reaction.
D condensations are reclaimed
Allow the gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A with implementation
Contacted in the identical gas absorption equipment of example 4, hydrogen fluoride and nitric acid absorbed under conditions of 56 DEG C of temperature with pressure 0.055MPa,
Obtain the described mixed acid containing hydrogen fluoride and nitric acid.Chemical analysis is determined, and it be in mass 16.7% that the mixed acid contains
Nitric acid and 5.6% hydrofluoric acid.
Claims (5)
1. a kind of method that the mixed acid containing nitric acid Yu hydrofluoric acid is reclaimed in pickle liquor from cold-rolling stainless steel, it is characterised in that
The step of methods described, is as follows：
A, concentration
Described cold-rolling stainless steel pickle liquor is allowed to be concentrated under conditions of 110~150 DEG C of temperature, until the pickling is useless
Liquid reaches NO3 -Content for by weight 4%~6%, Fe ion concentrations be by weight 1.56%~41.0%, pH value≤2 obtain
It is to a kind of oversaturated concentrating waste acid of nitrate and a kind of dilute with 2~3% hydrofluoric acid containing 4~6% nitric acid by weight
Acid condensation liquid；The concentration systems for using are the conventional triple effect evaporations of the evaporation equipment that assembling is made up of polytetrafluoroethylimpregnated impregnated graphite
System；
B, displacement reaction
The concentrated sulfuric acid, the nitrate supersaturation spent acid and dense sulphur are added in the nitrate supersaturation concentrating waste acid obtained toward step A
The weight ratio of acid is 1:0.2~0.6, it is well mixed, then under conditions of 100~130 DEG C and 0.1~0.3MPa of pressure of temperature
Reaction 0.5~8.5 hour；Equipment for replacing reaction is a kind of popular response being made of polytetrafluoroethylimpregnated impregnated graphite
Kettle；
The gas containing hydrogen fluoride and nitric acid produced in the course of reaction is escaped from the reaction system, and liquid phase is tied
Crystalline substance, separates, and obtains the mixing acid pickle of containing sulfate；
C, separation
The mixing acid pickle that step B is obtained is allowed to be carried out under conditions of -25 DEG C~25 DEG C of temperature with pressure 0.004-0.06MPa cold
But crystallize, obtained containing 45%~55% ferrous sulfate hydrate in mass through separation of solid and liquid, while it is with quality to obtain concentration
The sulphate of iron raffinate of meter 5%~15%；
D condensations are reclaimed
The gas containing hydrogen fluoride and nitric acid that step B obtains and the diluted acid condensate liquid obtained in step A are allowed with polytetrafluoroethyl-ne
Contacted in the gas absorption equipment that alkene impregnated graphite is made, inhaled under conditions of 40~60 DEG C of temperature with pressure 0.04-0.06MPa
Hydrogen fluoride and nitric acid are received, the described mixed acid containing hydrogen fluoride and nitric acid is obtained.
2. method according to claim 1, it is characterised in that in step, described nitrate supersaturation spent acid contains
Less than 0.40% other metal ions and nonmetallic ion and 2%~3% hydrofluoric acid by weight.
3. method according to claim 1, it is characterised in that in step C, described sulphate of iron raffinate first uses normal temperature
Water cooling, is then water-cooled to temperature -15~25 DEG C, then separation of solid and liquid with freezing, obtain the solid containing sulfate with it is dilute
Sulfate liquor, described dilute sulfuric acid mother liquor again returns to participate in displacement reaction in step B.
4. method according to claim 1, it is characterised in that in step D, described mixed acid contains and is in mass
14~17% nitric acid and 5~7% hydrofluoric acid.
5. method according to claim 1, it is characterised in that described polytetrafluoroethylimpregnated impregnated graphite is according to following sides
What method was prepared：
Graphite is placed in concentration in 55%~60% polytetrafluoroethyldispersion dispersion by weight, then pressure 0.3~
Impregnated 6~12 hours under conditions of 0.9MPa, 14 are sintered under conditions of 360~400 DEG C of temperature in the sintering furnace again after drying
~18 hours, obtain described polytetrafluoroethylimpregnated impregnated graphite.
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| CN104711617B (en) * | 2015-04-09 | 2017-09-26 | 南通晨光石墨设备有限公司 | A kind of renovation process of acid-washing waste acid |
| CN104828787B (en) * | 2015-04-09 | 2017-01-25 | 南通晨光石墨设备有限公司 | Process for separating and concentrating mixed acid |
| CN105385851A (en) * | 2015-11-04 | 2016-03-09 | 浙江盛达铁塔有限公司 | Treatment method of acid pickling waste liquid |
| CN105417828B (en) * | 2016-01-05 | 2018-06-12 | 中南大学 | A kind of heavy metal wastewater thereby resource recycle method containing low boiling point acid and its acid group |
| CN109467065B (en) * | 2018-11-30 | 2023-09-19 | 中冶南方工程技术有限公司 | Stainless steel mixed acid waste liquid regenerated acid equipment |
| CN109553152B (en) * | 2018-11-30 | 2021-09-10 | 中冶南方工程技术有限公司 | Stainless steel mixed acid waste liquid regenerated acid process |
| CN113003545A (en) * | 2021-02-23 | 2021-06-22 | 佛山市景嘉机电设备有限公司 | Method for recycling and treating iron-containing mixed acid waste liquid in steel industry |
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| JPH0657466A (en) * | 1992-08-07 | 1994-03-01 | Kooe Eng Kk | Method for recovering mixed acid of nitric acid with hydrofluoric acid or nitric acid, hydrofluoric acid from pickling waste water |
| CN1616717A (en) * | 2003-11-12 | 2005-05-18 | 张建海 | Technical treating method for recycling acid washing liquid of sulfuric acid |
| CN100369804C (en) * | 2006-05-29 | 2008-02-20 | 冶金部建筑研究总院上海分院 | Regenerating acid method by sulfuric acid substitution |
| CN101787537B (en) * | 2009-12-11 | 2011-11-16 | 北京天泰兴工程科技有限公司 | Method for recovering waste nitric-hydrofluoric acid from stainless steel annealing-pickling by micro- and negative-pressure evaporation and crystallization processes |
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