CN107460493A - A kind of recovery and treatment method of secondary metal pickle liquor - Google Patents
A kind of recovery and treatment method of secondary metal pickle liquor Download PDFInfo
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- CN107460493A CN107460493A CN201710537787.9A CN201710537787A CN107460493A CN 107460493 A CN107460493 A CN 107460493A CN 201710537787 A CN201710537787 A CN 201710537787A CN 107460493 A CN107460493 A CN 107460493A
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- pickle liquor
- recovery
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
Abstract
The present invention relates to intermetallic composite coating production technical field, discloses a kind of recovery and treatment method of secondary metal pickle liquor, comprises the following steps：（1）Prepare iron fluorine body crystal seed：The ferric flouride crystal containing the crystallization water being prepared, using dynamic method, crystalline deposit removes the residual metal composition in pickle liquor；（2）Eo-acid is added, is co-precipitated：Addition concentrated nitric acid is reacted with the metal waste paper and metal oxide contained in pickle liquor, obtained corresponding metal ion, and caused nitric oxide can be aoxidized further reacts generation nitric acid with water, add acidity, the water in waste liquid is reacted away simultaneously, the process of evaporation water removal is eliminated, has saved cost；（3）Pickle liquor recycles：The pickle liquor for removing co-precipitate carries out adsorption-edulcoration using activated zeolite, collects the recycling that pickle carries out intermetallic composite coating production.
Description
Technical field
The invention belongs to intermetallic composite coating production technical field, and in particular at a kind of recovery of secondary metal pickle liquor
Reason method.
Background technology
Because following global metals resources demand will be substantially increased, the whole world needs to rethink recycling for metal,
To mitigate the negative effect to environment.As emerging economy starts to gradually adopt the technology similar to country of OECD and life
Mode living, the metal demand amount in the following whole world will reach 3 to 9 times of whole world metal usage amount.The complicated metal production of recovery
The metal demand amount that product can solve and tackle rises violently the challenge brought.World's major part metal can be followed in the form of secondary metal
Ring utilizes, and industrially developed country's Secondary Metals Industry scale is big, and it is high that secondary metal recycles ratio.Because the market demand is strong
Strength, the development of China YouSe metal industry are advanced by leaps and bounds, and China has turned into the production and consumption big country of World Nonferrous Metals, China
Secondary Metals Industry have very important status in the development of world's Secondary Metals Industry.
Metal needs to be handled using substantial amounts of pickle liquor in recycling, and the overwhelming majority of these pickle liquors is all
Form pickling sludge stacking processing in a manner of neutralization precipitation, neutralization precipitation method needs to add substantial amounts of additive, medicament into
This is big, also has part using evaporation recovery acid solution, power consumption is high, and this causes huge not only for ecological environment and human health
Pressure, while be also a kind of significant wastage of resource.
The content of the invention
The purpose of the present invention is to be directed to the problem of existing, there is provided a kind of recycling side of secondary metal pickle liquor
Method, pickle liquor is subjected to recycling, has both reclaimed spent acid and got back metal byproducts.
The present invention is achieved by the following technical solutions：
A kind of recovery and treatment method of secondary metal pickle liquor, comprises the following steps：
（1）Prepare iron fluorine body crystal seed
By ammonium carbonate and water according to 1：4-5 weight ratio is configured to sal volatile, and iron chloride is with water according to 1：3-5 weight ratio
Be configured to ferric chloride solution, the ferric chloride solution for configuring to obtain is placed on magnetic stirring apparatus, mixing speed be 100-150 turn/
Minute, using titration outfit, the sal volatile of preparation is added drop-wise in ferric chloride solution, reaction proceeds to floccule and no longer increased
Add, add and account for reaction system quality 1-2% alcohol, after stirring, be filtered to remove liquid and obtain solid phase precipitation thing, using going
Ionized water and alcohol alternately cleaning 6 times, are filtered by vacuum, the hydrogen fluorine of 1.2-1.5 times of volume are added into obtained solid
Acid, evaporative crystallization, progress filtration drying produce the iron fluorine body crystal seed in 50-60 DEG C of water-bath after dissolving；
（2）Eo-acid is added, is co-precipitated
Concentrated nitric acid, sealing reaction are added into pickle liquor, addition is defined no longer to produce gas, reacts pickling after terminating
Waste liquid is heated to 40-50 DEG C, and the ratio that 3-5 grams of iron fluorine body crystal seed is added according to every kilogram of pickle liquor puts into freshly prepd iron fluorine
Body crystal seed, 4-6 hours are stood after stirring 20-30 minutes, carried out using particle size for the dolomite of 2-4 millimeters as filtrate
Filter, calcining recovery metal mixture after obtained solid filtrate is washed；
（3）Pickle liquor recycles
The activated zeolite that volume fraction is 1-2% is added into obtained filtrate, 40-50 points are stirred under 400-500 revs/min
Clock, 2-3 hours are stood, upper strata grease are pulled out, the lubricating oil that heating recovery is reused, the filtrate for reclaiming to obtain is with matter
The ratio that amount score ratio is 30-40%, which is added in new pickle, to be used, and the activated zeolite being filtrated to get, is 20- in mass concentration
Depressurize and filter after ultrasonic vibration 50-60 minutes in 30% alkali lye, obtain particulate matter and done immediately in 120-150 DEG C of electric heating air blast
3-5 hours are dried in dry case, recovery obtains activated zeolite.
As further improvement of these options, step（1）The middle alcohol quality concentration that uses is 60-70%, hydrofluoric acid
Mass concentration is 20-30%.
As further improvement of these options, step（2）Middle concentrated nitric acid mass concentration is 95-98%, and calcining heat is
400-450℃。
As further improvement of these options, step（3）Described in activated zeolite preparation method be：To naturally it boil
Stone flour is broken to 3-5 mm in size, and 10-12 hours are impregnated in the hydrochloric acid solution that mass concentration is 10-15%, are taken out at 50-60 DEG C
Baking oven in be dried, at 530-550 DEG C calcine 1.5-2.5 hours, 40-50 mesh is crushed to after cooling and is produced.
The present invention has advantages below compared with prior art：In order to solve in the existing recovery for metal pickle liquor not
The problem of reasonable, as neutralization precipitation method needs to add substantial amounts of additive, reagent cost is big, also has part to be reclaimed using evaporation
Acid solution, power consumption is high, and this causes huge pressure not only for ecological environment and human health, while is also a kind of pole of resource
Big the problem of wasting, the invention provides a kind of recovery and treatment method of secondary metal pickle liquor, comprise the following steps：
（1）Prepare iron fluorine body crystal seed：The ferric flouride crystal containing the crystallization water being prepared, using dynamic method, crystalline deposit removes
The residual metal composition gone in pickle liquor；（2）Eo-acid is added, is co-precipitated：Concentrated nitric acid is added with containing in pickle liquor
Metal waste paper and metal oxide reacted, obtained corresponding metal ion, and caused nitric oxide can
Further oxidation and water reaction generation nitric acid, add acidity, while the water in waste liquid is reacted away, and eliminate evaporation water removal
Process, cost is saved；（3）Pickle liquor recycles：The pickle liquor for removing co-precipitate is adsorbed using activated zeolite
Removal of impurities, collect the recycling that pickle carries out intermetallic composite coating production.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
A kind of recovery and treatment method of secondary metal pickle liquor, comprises the following steps：
（1）Prepare iron fluorine body crystal seed
By ammonium carbonate and water according to 1：4 weight ratio is configured to sal volatile, and iron chloride is with water according to 1：3 weight is than preparing
Into ferric chloride solution, the ferric chloride solution for configuring to obtain is placed on magnetic stirring apparatus, and mixing speed is 100 revs/min, is utilized
Titration outfit, the sal volatile of preparation is added drop-wise in ferric chloride solution, reaction proceeds to floccule and is not further added by, and addition accounts for
The alcohol of reaction system quality 1%, after stirring, it is filtered to remove liquid and obtains solid phase precipitation thing, use deionized water and alcohol
Alternately cleaning 6 times, are filtered by vacuum, and the hydrofluoric acid of 1.2 times of volumes are added into obtained solid, in 50 DEG C of water after dissolving
Evaporative crystallization in bath, carry out filtration drying and produce the iron fluorine body crystal seed；
（2）Eo-acid is added, is co-precipitated
Concentrated nitric acid, sealing reaction are added into pickle liquor, addition is defined no longer to produce gas, reacts pickling after terminating
Waste liquid is heated to 40 DEG C, and the ratio that 3 grams of iron fluorine body crystal seeds are added according to every kilogram of pickle liquor puts into freshly prepd iron fluorine body crystalline substance
Kind, stirring stands 4 hours after 20 minutes, is filtered, obtained as filtrate for the dolomite of 2-4 millimeters using particle size
Calcining recovery metal mixture after solid filtrate is washed；
（3）Pickle liquor recycles
The activated zeolite that volume fraction is 1% is added into obtained filtrate, is stirred 40 minutes under 400 revs/min, it is small to stand 2
When, upper strata grease is pulled out, the lubricating oil that heating recovery is reused, reclaim obtained filtrate using mass fraction ratio as
30% ratio, which is added in new pickle, to be used, the activated zeolite being filtrated to get, the ultrasound in the alkali lye that mass concentration is 20%
Concussion is depressurized after 50 minutes and filtered, and is obtained particulate matter and is dried 3 hours in 120 DEG C of electric drying oven with forced convection immediately, is reclaimed
To activated zeolite.
As further improvement of these options, step（1）The middle alcohol quality concentration used is 60%, hydrofluoric acid matter
It is 20% to measure concentration.
As further improvement of these options, step（2）Middle concentrated nitric acid mass concentration is 95%, calcining heat 400
℃。
As further improvement of these options, step（3）Described in activated zeolite preparation method be：To naturally it boil
Stone flour is broken to 3-5 mm in size, impregnates 10 hours, is taken out in 50 DEG C of baking oven in the hydrochloric acid solution that mass concentration is 10%
It is dried, is calcined 1.5 hours at 530 DEG C, 40 mesh are crushed to after cooling and are produced.
Embodiment 2
A kind of recovery and treatment method of secondary metal pickle liquor, comprises the following steps：
（1）Prepare iron fluorine body crystal seed
By ammonium carbonate and water according to 1：4.5 weight ratio is configured to sal volatile, and iron chloride is with water according to 1：3.5 weight ratio
Ferric chloride solution is configured to, the ferric chloride solution for configuring to obtain is placed on magnetic stirring apparatus, and mixing speed is 120 revs/min,
Using titration outfit, the sal volatile of preparation is added drop-wise in ferric chloride solution, reaction proceeds to floccule and is not further added by, and adds
Enter to account for the alcohol of reaction system quality 1%, after stirring, be filtered to remove liquid and obtain solid phase precipitation thing, using deionized water and
Alcohol alternately cleaning 6 times, are filtered by vacuum, the hydrofluoric acid of 1.4 times of volumes are added into obtained solid, 55 after dissolving
Evaporative crystallization in DEG C water-bath, carry out filtration drying and produce the iron fluorine body crystal seed；
（2）Eo-acid is added, is co-precipitated
Concentrated nitric acid, sealing reaction are added into pickle liquor, addition is defined no longer to produce gas, reacts pickling after terminating
Waste liquid is heated to 45 DEG C, and the ratio that 4 grams of iron fluorine body crystal seeds are added according to every kilogram of pickle liquor puts into freshly prepd iron fluorine body crystalline substance
Kind, stirring stands 5 hours after 25 minutes, is filtered, obtained as filtrate for the dolomite of 2-4 millimeters using particle size
Calcining recovery metal mixture after solid filtrate is washed；
（3）Pickle liquor recycles
The activated zeolite that volume fraction is 1.5% is added into obtained filtrate, is stirred 45 minutes under 450 revs/min, is stood
2.5 hours, upper strata grease is pulled out, the lubricating oil that heating recovery is reused, the filtrate for reclaiming to obtain is with mass fraction
Than being added in new pickle the activated zeolite for using, being filtrated to get for 35% ratio, in the alkali lye that mass concentration is 25%
Ultrasonic vibration depressurizes suction filtration after 55 minutes, obtain particulate matter and dried 4 hours in 135 DEG C of electric drying oven with forced convection immediately, returned
Receipts obtain activated zeolite.
As further improvement of these options, step（1）The middle alcohol quality concentration used is 65%, hydrofluoric acid matter
It is 25% to measure concentration.
As further improvement of these options, step（2）Middle concentrated nitric acid mass concentration is 96%, calcining heat 430
℃。
As further improvement of these options, step（3）Described in activated zeolite preparation method be：To naturally it boil
Stone flour is broken to 3-5 mm in size, impregnates 11 hours, is taken out in 55 DEG C of baking oven in the hydrochloric acid solution that mass concentration is 13%
It is dried, is calcined 2.0 hours at 540 DEG C, 45 mesh are crushed to after cooling and are produced.
Embodiment 3
A kind of recovery and treatment method of secondary metal pickle liquor, comprises the following steps：
（1）Prepare iron fluorine body crystal seed
By ammonium carbonate and water according to 1：5 weight ratio is configured to sal volatile, and iron chloride is with water according to 1：5 weight is than preparing
Into ferric chloride solution, the ferric chloride solution for configuring to obtain is placed on magnetic stirring apparatus, and mixing speed is 150 revs/min, is utilized
Titration outfit, the sal volatile of preparation is added drop-wise in ferric chloride solution, reaction proceeds to floccule and is not further added by, and addition accounts for
The alcohol of reaction system quality 2%, after stirring, it is filtered to remove liquid and obtains solid phase precipitation thing, use deionized water and alcohol
Alternately cleaning 6 times, are filtered by vacuum, and the hydrofluoric acid of 1.5 times of volumes are added into obtained solid, in 60 DEG C of water after dissolving
Evaporative crystallization in bath, carry out filtration drying and produce the iron fluorine body crystal seed；
（2）Eo-acid is added, is co-precipitated
Concentrated nitric acid, sealing reaction are added into pickle liquor, addition is defined no longer to produce gas, reacts pickling after terminating
Waste liquid is heated to 50 DEG C, and the ratio that 5 grams of iron fluorine body crystal seeds are added according to every kilogram of pickle liquor puts into freshly prepd iron fluorine body crystalline substance
Kind, stirring stands 6 hours after 30 minutes, is filtered, obtained as filtrate for the dolomite of 2-4 millimeters using particle size
Calcining recovery metal mixture after solid filtrate is washed；
（3）Pickle liquor recycles
The activated zeolite that volume fraction is 2% is added into obtained filtrate, is stirred 50 minutes under 500 revs/min, it is small to stand 3
When, upper strata grease is pulled out, the lubricating oil that heating recovery is reused, reclaim obtained filtrate using mass fraction ratio as
40% ratio, which is added in new pickle, to be used, the activated zeolite being filtrated to get, the ultrasound in the alkali lye that mass concentration is 30%
Concussion is depressurized after 60 minutes and filtered, and is obtained particulate matter and is dried 5 hours in 150 DEG C of electric drying oven with forced convection immediately, is reclaimed
To activated zeolite.
As further improvement of these options, step（1）The middle alcohol quality concentration used is 70%, hydrofluoric acid matter
It is 30% to measure concentration.
As further improvement of these options, step（2）Middle concentrated nitric acid mass concentration is 98%, calcining heat 450
℃。
As further improvement of these options, step（3）Described in activated zeolite preparation method be：To naturally it boil
Stone flour is broken to 3-5 mm in size, impregnates 12 hours, is taken out in 60 DEG C of baking oven in the hydrochloric acid solution that mass concentration is 15%
It is dried, is calcined 2.5 hours at 550 DEG C, 50 mesh are crushed to after cooling and are produced.
Comparative example 1
With being distinguished as embodiment 1, pickle liquor is reclaimed using neutralization precipitation method.
Comparative example 2
With being distinguished as embodiment 2, pickle liquor is reclaimed using heating vaporization.
Comparative example 3
With being distinguished as embodiment 3, pickle liquor is reclaimed using electrolysis.
Contrast test
Respectively according to embodiment 1-3 and comparative example 1-3 method recycle secondary metal pickle liquor, by pickling result with
It is as a result as shown in the table and efficiency cost is compared：
| Project | Metal recovery rate in pickle liquor（%） | The sour rate of recovery in pickle liquor（%） | Resource weight utilization rate improves（%） | It is cost-effective（%） |
| Embodiment 1 | 85.6 | 46.7 | 52.3 | 38.9 |
| Embodiment 2 | 87.2 | 47.3 | 53.6 | 40.4 |
| Embodiment 3 | 86.4 | 46.9 | 52.7 | 39.6 |
| Comparative example 1 | 34.9 | 0 | Control | Control |
| Comparative example 2 | 21.7 | 15.8 | 12.5 | 12.7 |
| Comparative example 3 | 47.6 | 8.6 | 18.4 | 9.3 |
By relatively：The recovery and treatment method of a kind of secondary metal pickle liquor provided by the invention, by pickle liquor
Recycling is carried out, spent acid had both been reclaimed and has got back metal byproducts, and saved cost.
Claims (4)
1. a kind of recovery and treatment method of secondary metal pickle liquor, it is characterised in that comprise the following steps：
（1）Prepare iron fluorine body crystal seed
By ammonium carbonate and water according to 1：4-5 weight ratio is configured to sal volatile, and iron chloride is with water according to 1：3-5 weight ratio
Be configured to ferric chloride solution, the ferric chloride solution for configuring to obtain is placed on magnetic stirring apparatus, mixing speed be 100-150 turn/
Minute, using titration outfit, the sal volatile of preparation is added drop-wise in ferric chloride solution, reaction proceeds to floccule and no longer increased
Add, add and account for reaction system quality 1-2% alcohol, after stirring, be filtered to remove liquid and obtain solid phase precipitation thing, using going
Ionized water and alcohol alternately cleaning 6 times, are filtered by vacuum, the hydrogen fluorine of 1.2-1.5 times of volume are added into obtained solid
Acid, evaporative crystallization, progress filtration drying produce the iron fluorine body crystal seed in 50-60 DEG C of water-bath after dissolving；
（2）Eo-acid is added, is co-precipitated
Concentrated nitric acid, sealing reaction are added into pickle liquor, addition is defined no longer to produce gas, reacts pickling after terminating
Waste liquid is heated to 40-50 DEG C, and the ratio that 3-5 grams of iron fluorine body crystal seed is added according to every kilogram of pickle liquor puts into freshly prepd iron fluorine
Body crystal seed, 4-6 hours are stood after stirring 20-30 minutes, carried out using particle size for the dolomite of 2-4 millimeters as filtrate
Filter, calcining recovery metal mixture after obtained solid filtrate is washed；
（3）Pickle liquor recycles
The activated zeolite that volume fraction is 1-2% is added into obtained filtrate, 40-50 points are stirred under 400-500 revs/min
Clock, 2-3 hours are stood, upper strata grease are pulled out, the lubricating oil that heating recovery is reused, the filtrate for reclaiming to obtain is with matter
The ratio that amount score ratio is 30-40%, which is added in new pickle, to be used, and the activated zeolite being filtrated to get, is 20- in mass concentration
Depressurize and filter after ultrasonic vibration 50-60 minutes in 30% alkali lye, obtain particulate matter and done immediately in 120-150 DEG C of electric heating air blast
3-5 hours are dried in dry case, recovery obtains activated zeolite.
A kind of 2. recovery and treatment method of secondary metal pickle liquor as claimed in claim 1, it is characterised in that step（1）
The middle alcohol quality concentration used is 60-70%, and hydrofluoric acid mass concentration is 20-30%.
A kind of 3. recovery and treatment method of secondary metal pickle liquor as claimed in claim 1, it is characterised in that step（2）
Middle concentrated nitric acid mass concentration is 95-98%, and calcining heat is 400-450 DEG C.
A kind of 4. recovery and treatment method of secondary metal pickle liquor as claimed in claim 1, it is characterised in that step（3）
Described in activated zeolite preparation method be：Natural zeolite is crushed to 3-5 mm in size, in the salt that mass concentration is 10-15%
10-12 hours are impregnated in acid solution, takes out and is dried in 50-60 DEG C of baking oven, 1.5- is calcined at 530-550 DEG C
2.5 hours, 40-50 mesh is crushed to after cooling and is produced.
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| CN201710537787.9A CN107460493A (en) | 2017-07-04 | 2017-07-04 | A kind of recovery and treatment method of secondary metal pickle liquor |
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| CN201710537787.9A CN107460493A (en) | 2017-07-04 | 2017-07-04 | A kind of recovery and treatment method of secondary metal pickle liquor |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003490A (en) * | 2014-05-19 | 2014-08-27 | 上海大学 | Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal |
| CN104250820A (en) * | 2013-06-27 | 2014-12-31 | 宝钢不锈钢有限公司 | Method and apparatus for regenerating all acid of stainless steel pickling waste liquid |
| CN104944665A (en) * | 2015-06-19 | 2015-09-30 | 浙江大学 | Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid |
-
2017
- 2017-07-04 CN CN201710537787.9A patent/CN107460493A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250820A (en) * | 2013-06-27 | 2014-12-31 | 宝钢不锈钢有限公司 | Method and apparatus for regenerating all acid of stainless steel pickling waste liquid |
| CN104003490A (en) * | 2014-05-19 | 2014-08-27 | 上海大学 | Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal |
| CN104944665A (en) * | 2015-06-19 | 2015-09-30 | 浙江大学 | Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid |
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Application publication date: 20171212 |