CN1211504C - Nickel-containing iron trichloride etching effluent extraction and separation method - Google Patents
Nickel-containing iron trichloride etching effluent extraction and separation method Download PDFInfo
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- CN1211504C CN1211504C CN 03131945 CN03131945A CN1211504C CN 1211504 C CN1211504 C CN 1211504C CN 03131945 CN03131945 CN 03131945 CN 03131945 A CN03131945 A CN 03131945A CN 1211504 C CN1211504 C CN 1211504C
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- 238000000605 extraction Methods 0.000 title claims abstract description 99
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000005530 etching Methods 0.000 title claims abstract description 57
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title abstract description 15
- 238000000926 separation method Methods 0.000 title abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 114
- 239000007788 liquid Substances 0.000 claims abstract description 77
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000012074 organic phase Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 50
- 239000003350 kerosene Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- -1 phosphate diformazan heptyl ester Chemical class 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- DBLHYLDWZSNRBI-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(=O)(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(=O)(O)(O)O DBLHYLDWZSNRBI-UHFFFAOYSA-N 0.000 claims description 3
- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 67
- 229910052742 iron Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 239000000284 extract Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
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Abstract
The present invention relates to an extraction and separation method of waste nickel containing iron trichloride etching liquid for etching iron family metal, which comprises the following steps that (1) a kind of waste nickel containing FeCl3 liquid is provided; (2) Cl2 is led in the waste liquid, and the waste liquid is oxidated under an acid condition to acquire first waste liquid; (3) NiCl2 is added to the first waste liquid, and second waste liquid is acquired; (4) a first extraction device and a first organic extraction agent are provided; (5) the first organic extraction agent is introduced into the first extraction device; (6) the second waste liquid is introduced into the first extraction device, separated and extracted, FeCl3 is dissolved in an organic phase, and NiCl2 is dissolved in a water phase; (7) the organic phase is washed in water to acquired a FeCl3 solution; a second extraction device and a second organic extraction agent are provided; (9) the second organic extraction agent and the water phase oxidated by H2O2 are introduced into the second extraction device, and NiCl2 is extracted, purified and concentrated to acquire NiCl2 crystals. The present invention thoroughly separates iron and nickel in the waste etching liquid, reduces the cost and also generates nickel chloride with high recovery value.
Description
Technical field
The present invention relates to a kind of treatment process of chemical method etching waste liquor of metallic substance, the extraction separating method of the Ni from waste etching FeCl 3 solution containing of particularly a kind of etching iron family metal or refractory metal.
Background technology
Current in the shadow mask production process of printed-wiring board (PWB) or indicating meter and televisor, often etching iron family metal or refractory metal (as nickel) and form shadow mask adopt the high density ferric chloride aqueous solutions as etching solution, because FeCl simultaneously also essentially
3Whole etching reaction is leniently carried out and can not produce bubble, thereby make mask surface fine and close more, quality is better.
But, in etching process, iron trichloride etched metallic iron of meeting and nickel are reduced to ferrous chloride, and metallic nickel also enters in the etching solution with the form of nickelous chloride, along with etching reaction continue carry out, the concentration of iron trichloride constantly reduces, etching efficiency also can descend thereupon, for fear of the decline of etching efficiency, must periodically in reactive system, add fresh iron trichloride etching solution to replace remaining etching waste liquor, contain a considerable amount of Fe in this etching waste liquor
2+, Ni
2+And the Fe of a small amount of (about 15%)
3+, Fe
2+Can regenerate by chlorine oxidation, and Ni
2+Then must adopt other method to remove.
The regeneration method of etching waste liquor commonly used is the iron powder reducing method, uses iron exactly, and is that high-quality excess iron powder is replaced the Ni in the etching waste liquor
2+, lose (the part iron powder that also contains input usually in this waste residue) and make metallic nickel become waste residue, and the Fe in the waste liquid
2+Then become Fe with chlorine oxidation
3+This method of replacing has following weak point: the iron powder of required employing costs an arm and a leg; This technological process is to replace nickel with iron earlier, uses chlorine oxidation Fe again
2+, thereby the Fe of about 15% in the waste liquid
3+Can be reduced into Fe earlier
2+, be reoxidised into Fe with chlorine then
3+, this reduction-oxidation process has obviously been wasted the consumption of iron powder and chlorine; The iron that contains in the waste residue also belongs to the row of waste.Thereby this method regeneration etching solution cost is too high, and the utility value again of ferronickel waste residue is lower.Simultaneously, adopt 1 ton of waste liquid of iron replacement method can produce the new liquid of about 1.5 tons iron trichloride, so promptly consumed raw material, and the about 0.5 ton iron trichloride etching solutions that get do not need more, waste in rain, and after plural number time reclaims waste liquid, obviously go up a great problem that is treated as of long iron trichloride at double.
Summary of the invention
The objective of the invention is to overcome weak point of the prior art, and provide a kind of extraction separating method of Ni from waste etching FeCl 3 solution containing, this method can fully guarantee the nickel in the etching waste liquor, the separation of iron, the abundant regeneration that reaches iron trichloride is used, and cost is low, seldom increases liquor ferri trichloridi.
Purpose of the present invention can realize through following scheme.
The extraction separating method of Ni from waste etching FeCl 3 solution containing, its main points are, comprise the steps:
1, provide a kind of Ni from waste etching FeCl 3 solution containing,
2, in waste liquid, feed chlorine and under acidic conditions, carry out the oxidizing reaction waste liquid of winning,
3, in first waste liquid, add nickelous chloride and get second waste liquid,
4, provide a kind of first extraction plant, a kind of first organic extractant,
5, first organic extractant is imported first extraction plant,
6, second waste liquid is imported first extraction plant and carry out separating and extracting, wherein iron trichloride is dissolved in organic phase, and nickelous chloride is soluble in the aqueous phase,
7, water cleans organic phase and gets the high density liquor ferri trichloridi,
8, provide a kind of second extraction plant, a kind of second organic extractant,
9, with second organic extractant and use H
2O
2The water of oxidation imports the purification by liquid extraction that second extraction plant carries out nickelous chloride, and gets the nickelous chloride crystal through condensing crystal.
Because contain a considerable amount of Fe in the waste liquid
2+, Ni
2+And the Fe of a small amount of (about 15%)
3+, by in waste liquid, feeding chlorine Fe
2+Be oxidized to Fe
3+Thereby, the waste liquid of winning.
In order to prevent in the extraction process because iron trichloride is caused the ionic concn of aqueous phase to reduce by organic extractant phase, extractive reaction is thorough inadequately, need in first waste liquid, to add nickelous chloride when extraction or before extracting and get second waste liquid, in order to increase the concentration of the chlorion in the waste liquid, thereby the collection that makes extractive reaction be partial to iron trichloride and organic phase is closed, and improves percentage extraction.
The novel process that interpolation first organic extractant iron trichloride carries out extracting and separating in first extraction plant that the present invention proposes never to have in the prior art replaces the iron replacement method, first organic extractant only need satisfy and the iron trichloride in the waste liquid is had the extraction function gets final product, thereby the kind of organic extractant is not limited, for example can be secondary octanol, methyl iso-butyl ketone (MIBK) etc.
As for extraction plant is the conventional extraction equipment that uses, as tower extractor, box-type extractor.
Usually adopting organic extractant that metal or metal-salt are extracted needs carry out in the acid-reaction system, difference only be the acid of adopting which kind of acid or adopting which kind of concentration.The present invention carries out under acidic conditions for the realization response system, can add HCl in waste liquid, makes it that concentration is 0.2～1.8% in the waste liquid reaction system, and best concentration is 0.5%.
The present invention also carries out wash-out with water to the iron trichloride of organic phase, thereby iron trichloride is separated with organic phase, and the extraction equipment that has in the prior art generally all has the function that extracts simultaneously with wash-out.
Recovery for the nickelous chloride of aqueous phase, what the present invention adopted is method of extraction, extraction equipment can be identical with the equipment of extraction iron(ic) chloride, and the function that second organic extractant then only need satisfy having separating and extracting between the nickelous chloride of aqueous phase and other content gets final product.
This novel process has reached following beneficial technical effects:
Earlier to the Fe in the waste liquid
2+Use chlorine oxidation, because lacked original Fe
3+The chlorine that reduction-oxidation is required, thereby chlorine amount ratio iron replacement method is few, cost reduces;
Whole technology need not expensive iron powder, and cost significantly reduces;
Adopt organic extractant that iron trichloride is extracted, thereby iron trichloride is separated thoroughly with nickelous chloride, the content of Ni in original etching waste liquor is about 1%～3%, and the content of the Ni in the high density liquor ferri trichloridi after the extraction is less than 0.01%, the content nearly approximately 0.1% of Ni in original iron replacement method gained liquor ferri trichloridi, and the concentration of the iron trichloride washed out of present method can reach more than 38%, as seen it is comparatively thorough that this technology makes iron, nickel separation in the waste liquid, fully realized the regeneration of iron trichloride in the etching waste liquor.
And present method is that 1 ton waste liquid is produced 1 ton the new liquid of iron trichloride basically, do not waste raw material, also the problem that can not exist unnecessary liquor ferri trichloridi to handle.
Generally speaking, this extraction separating method greatly reduces cost in the isolating while that fully guarantees iron, nickel in the etching waste liquor.
And then, on iron, nickel separate completely the basis, water is carried out extractive crystallization and regenerate also highlyer the nickelous chloride product than iron trichloride economic worth, fully realized the utilization again of refuse, thereby further reduced cost, improved economic benefit, this is of the present invention one unexpected technique effect.
Moreover the present invention adopts water that iron trichloride is carried out wash-out, can not introduce new ion, and process cost is low, and this is another unexpected technique effect of the present invention.
Purpose of the present invention also can realize through following scheme.
Include the organophosphorus extraction agent in the component of first organic extractant.
The organophosphorus extraction agent be a class can with metal ion or its esters chelating or coordinate oil soluble organo phosphorous compounds, the organophosphorus extraction agent becomes extracted species with iron trichloride Chemical bond in the etching waste liquor and is dissolved in the organic phase, its enrichment combination rate height, thereby percentage extraction height, so the iron in the etching waste liquor, the good separating effect of nickel, and then the regeneration rate height of iron trichloride, cost just reduces.
The organophosphorus extraction agent mainly contains neutral phosphonic type and acidic phosphorus type, the neutral phosphonic type has tributyl phosphate, and acidic phosphorus type has di-(2-ethylhexyl)phosphoric acid (code name P204), 2-ethylhexyl phosphoric acid single 2-ethyl ethyl ester (code name P507), two (1-first heptyl) phosphoric acid (code name P215).
The present invention also is
The organophosphorus extraction agent is specially methyl acid phosphate diformazan heptyl ester (code name: P350).
Molecular formula is:
Methyl acid phosphate diformazan heptyl ester belongs to neutral organophosphorus extractant, and (general formula is XYZPO; X; Y; Z is different groups); they are that ligand complex reaction by metal and phosphoryl Sauerstoffatom realizes to the extraction of metal-salt; because the electric density of phosphoryl Sauerstoffatom is strong in the methyl acid phosphate diformazan heptyl ester; thereby it is strong to the coordination ability of molysite; and then extracting power increases; test shows; adopt methyl acid phosphate diformazan heptyl ester as the percentage extraction height of extraction agent to molysite; thereby make the concentration of the iron trichloride behind the wash-out can reach more than 38%; industry standard 43.5% from the finished product etching solution is comparatively approaching. so it is low to be concentrated into the cost of finished product.
This organophosphorus extraction agent or can also be that (X, Y, Z are OC to tributyl phosphate
4H
9).
Also include kerosene in the component of first organic extractant.
Kerosene plays dilution, and it can increase the flowability of organic phase, prevents that organic phase from coming together too thickly behind the iron trichloride, is unfavorable for the carrying out of follow-up reextraction.
Adding kerosene simultaneously can increase the volume of organic phase, and extraction efficiency E (representing with percentage) is relevant with the volume of organic phase, sees following formula for details:
Wherein, D represents the ratio of total concn with the total concn of aqueous phase extract of extract in the organic phase (iron trichloride), V
WaterThe volume of expression water, V
HaveThe volume of expression organic phase if visible D fixes, reduces V
Water/ V
HavePromptly increase the volume of organic phase, then can improve extraction efficiency, thereby increase the volume that certain kerosene can increase organic phase, thereby further reduce cost, but the raising of efficient is again relative, if the given volume of organic phase, the shared ratio of kerosene is many more, obviously will reduce the consumption of methyl acid phosphate diformazan heptyl ester and reduce extraction efficiency, thereby the used in amounts of methyl acid phosphate diformazan heptyl ester and kerosene is wanted certain ratio, the inventor the results showed, adopt following ratio, when guaranteeing good percentage extraction, can reach the purpose of saving cost preferably.
The weight ratio of each component is in first extraction agent: methyl acid phosphate diformazan heptyl ester 25%～45%, kerosene 55%～75%.
Wherein Zui Jia ratio is
Methyl acid phosphate diformazan heptyl ester 35%, kerosene 65%.
Purpose of the present invention further can also realize through following scheme.
The waste liquid and first organic extractant volume proportion when extraction need satisfy the abundant dissolving of iron trichloride in first organic extractant, for example extract and to make iron trichloride over-saturation in first organic extractant by the volume proportion of the waste liquid of the first about 5 parts organic extractant and 1 part, the consumption of first organic extractant of this moment is less, can certainly increase the consumption of first organic extractant, because D fixes, V
Water/ V
HaveMore little, extraction efficiency E is good more, but cost is increased conventional span:
The volume ratio of the waste liquid and first organic extractant is 1: 5～8.
With the volume ratio of the waste liquid and first organic extractant be 1: 6 be the best.
The inventor is according to experience and the actual operation of carrying out, and the step of first waste liquid importing extraction plant being carried out separating and extracting is specific as follows:
First waste liquid is imported the counter-current extraction that carries out 12 grades in the extraction plant to be separated.
In order to improve extraction efficiency, present method can be taked multi-stage counter current extraction, be that waste liquid enters from head end, discharge by end at last that organic phase then enters from end by at different levels, by at different levels and discharge from head end, can increase the duration of contact of extraction agent and extract like this, thereby guarantee that extract can be extracted more thoroughly, and the consumption of organic phase is also little, thereby improve the content of the iron trichloride of finished product, and then save cost.
Many more as for the progression in the extraction plant, it is thoroughly more that iron, nickel separate, but running cost equally also increases together together with progression, and progression very little, may divide defection not thorough, thereby adopts 12 grades extraction plant can reach best aspect cost performance.
When the present invention is also that further the adding nickelous chloride gets second waste liquid in first waste liquid,
First waste liquid and concentration are that the volume ratio of 180g/l nickel chloride solution is 1.5: 1.
Under the condition of this concentration and volume ratio, can satisfy the requirement of aqueous phase, thereby the collection that improves iron trichloride and organic phase is closed degree, and then improve percentage extraction chlorine ion concentration.
The present invention also comprises the steps:
(1) incite somebody to action first solution that water simmer down to partly contains nickelous chloride 180g/l,
(2) be to mix the two at 1.5: 1 to get second waste liquid according to first waste liquid and the volume ratio of first solution,
(3) remaining water is adopted after with the hydrogen peroxide deep oxidation second organic extractant carry out the purification by liquid extraction of nickelous chloride in second extraction plant, and through condensing crystal and the nickelous chloride crystal product.
It is required that the nickelous chloride that the step order of this increase is reclaimed is used to satisfy present method earlier, thereby reduce the loss of raw material, and then general's nickelous chloride crystal product redundantly reaches the purpose of dual saving cost to realize its another economic worth.
And the extraction present technique field to nickelous chloride has a lot of sophisticated technologies in present method, the invention provides following scheme:
Second organic extractant is specially 20% N235,10% secondary octanol, 70% kerosene.
In sum, the present invention has following advantage compared to prior art: proposed to adopt extraction to come the novel method of iron, nickel etc. in the release etch waste liquid, this method is in the isolating while that fully guarantees iron, nickel in the etching waste liquor, greatly reduce cost, the problem that can exist unnecessary liquor ferri trichloridi to handle has not also generated the high nickelous chloride of recovery value simultaneously.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 1.
Fig. 2 is the process flow sheet of the embodiment of the invention 2, embodiment 3, most preferred embodiment.
Embodiment
Below in conjunction with embodiment the present invention is described in more detail.
Embodiment 1:
The extraction separating method of Ni from waste etching FeCl 3 solution containing as shown in Figure 1 comprises the steps:
1, provides a kind of etching waste liquor, wherein FeCl
333%, FeCl
27.7 ± 3%, Ni3%,
2, in the container of etching waste liquor is housed, feed chlorine and carry out oxidizing reaction, and add HCl and in acid system, carry out, and the concentration of HCl is 1.8% in the waste liquid to guarantee entire reaction, and the waste liquid (FeCl that wins
2≤ 0.1%),
3, in first waste liquid by the volume ratio of first waste liquid and nickel chloride solution be add at 1.5: 1 nickelous chloride (180g/l) second waste liquid,
4, provide a kind of first tower extractor, a kind of first organic extractant,
Wherein, first organic extractant contains tributyl phosphate 25%, kerosene 75%,
5, be that 1: 8 proportioning imports the first tower extractor with first organic extractant by the volume ratio of the waste liquid and first organic extractant,
6, second waste liquid is imported the first tower extractor and carry out 6 grades counter-current separation extraction, wherein iron trichloride is dissolved in organic phase, and nickelous chloride is soluble in the aqueous phase,
7, extract organic phase, water cleans and divides 6 grades organic phase advanced the ground wash-out, iron trichloride concentration be 30%, FeCl
2＜0.1%, the solution of Ni＜0.03% is concentrated into this solution high temperature 43.5% industrial etching solution;
8, provide a kind of second tower extractor, a kind of second organic extractant that contains 20% N235,10% secondary octanol, 70% kerosene,
9, add H at aqueous phase
2O
2Carry out deep oxidation, make the Fe of aqueous phase
3+＜0.001%, then water is imported the second tower extractor, through 4 stage countercurrent purification by liquid extractions, make NiCl
2Contain Fe＜0.005g/l in the concentrated solution, Cu＜0.005g/l, Zn＜0.01g/l, and through condensing crystal and industrial nickelous chloride crystal product, the raffinate otherwise processed.
It is same as the prior art that present embodiment is not stated part.
Embodiment 2:
The extraction separating method of Ni from waste etching FeCl 3 solution containing as shown in Figure 2 comprises the steps:
1, provides a kind of etching waste liquor, wherein FeCl
333%, FeCl
27.7 ± 3%, Ni3%,
2, in the container of etching waste liquor is housed, feed chlorine and carry out oxidizing reaction, and add HCl and in acid system, carry out, and the concentration of HCl is 0.2% to guarantee entire reaction, and the waste liquid of winning,
3, in first waste liquid by the volume ratio of first waste liquid and nickel chloride solution be add at 1.5: 1 nickelous chloride (180g/l) the second waste liquid (FeCl
2≤ 0.1%),
4, provide a kind of first box-type extractor, a kind of first organic extractant,
Wherein, first organic extractant contains methyl acid phosphate diformazan heptyl ester 45%, kerosene 55%,
5, be that 1: 6 proportioning imports first box-type extractor with first organic extractant with the volume ratio of the waste liquid and first organic extractant,
6, then second waste liquid is imported first box-type extractor and carry out 13 grades counter-current separation extraction, wherein iron trichloride is dissolved in organic phase, and nickelous chloride is soluble in the aqueous phase,
7, extract organic phase, water cleans and divides 13 grades organic phase advanced the ground wash-out, iron trichloride concentration be 34%, FeCl
2＜0.1%, the solution of Ni＜0.03% is concentrated into this solution high temperature 43.5% industrial etching solution;
8, extract water, the water simmer down to of part is contained first solution of nickelous chloride 180g/l, this first solution is used for the step 3 of present method as nickel chloride solution.
9, provide a kind of second box-type extractor, a kind of second organic extractant that contains 20% N235,10% secondary octanol, 70% kerosene,
10, in remaining water, add H
2O
2Carry out deep oxidation, make the Fe of aqueous phase
3+＜0.001%, import second box-type extractor then, through 4 stage countercurrent purification by liquid extractions, make NiCl
2Contain Fe＜0.005g/l in the concentrated solution, Cu＜0.005g/l, Zn＜0.01g/l, and through condensing crystal and industrial nickelous chloride crystal product, the raffinate otherwise processed.
All the other processing steps are identical with embodiment 1 among the present invention.
Embodiment 3:
The extraction separating method of Ni from waste etching FeCl 3 solution containing as shown in Figure 2 comprises the steps:
First organic extractant contains methyl acid phosphate diformazan heptyl ester 25%, kerosene 75%.
All the other processing steps are identical with embodiment 2 among the present invention.
Most preferred embodiment:
The extraction separating method of Ni from waste etching FeCl 3 solution containing as shown in Figure 2 comprises the steps:
The concentration that adds HCl in the container of etching waste liquor is housed is 0.5%;
First organic extractant contains methyl acid phosphate diformazan heptyl ester 35%, kerosene 65%;
Second waste liquid is imported first extraction plant carry out 12 grades counter-current separation extraction, wherein iron trichloride is dissolved in organic phase, and nickelous chloride is soluble in the aqueous phase;
Water clean to divide 12 grades organic phase advanced the ground wash-out, concentration is 38% liquor ferri trichloridi.
All the other processing steps are identical with embodiment 2 among the present invention.
Claims (11)
1, the extraction separating method of Ni from waste etching FeCl 3 solution containing is characterized in that, comprises the steps:
(1) provide a kind of Ni from waste etching FeCl 3 solution containing,
(2) in waste liquid, feed chlorine and under acidic conditions, carry out the oxidizing reaction waste liquid of winning,
(3) in first waste liquid, add nickelous chloride and get second waste liquid,
(4) provide a kind of first extraction plant, a kind of first organic extractant,
(5) first organic extractant is imported first extraction plant,
(6) second waste liquid is imported first extraction plant and carry out separating and extracting, wherein iron trichloride is dissolved in organic phase, and nickelous chloride is soluble in the aqueous phase,
(7) water cleans organic phase and gets the high density liquor ferri trichloridi,
(8) provide a kind of second extraction plant, a kind of second organic extractant,
(9) with second organic extractant and use H
2O
2The water of oxidation imports the purification by liquid extraction that second extraction plant carries out nickelous chloride, and gets the nickelous chloride crystal through condensing crystal.
2, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that, includes the organophosphorus extraction agent in the component of first organic extractant.
3, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 2 is characterized in that, the organophosphorus extraction agent is specially methyl acid phosphate diformazan heptyl ester.
4, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that, also includes kerosene in the component of first organic extractant.
5, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 4 is characterized in that, the weight ratio of each component is in first extraction agent: methyl acid phosphate diformazan heptyl ester 25%～45%, kerosene 55%～75%.
6, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 5 is characterized in that, the weight ratio of each component is in first extraction agent: methyl acid phosphate diformazan heptyl ester 35%, kerosene 65%.
7, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that, the volume ratio of the waste liquid and first organic extractant is 1: 6.
8, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that, first waste liquid is imported the counter-current extraction that carries out 12 grades in the extraction plant separate.
9, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterized in that, step wherein (3) adds nickelous chloride when getting second waste liquid in first waste liquid, first waste liquid and concentration are that the volume ratio of 180g/l nickel chloride solution is 1.5: 1.
10, the extraction separating method of Ni from waste etching FeCl 3 solution containing according to claim 9 is characterized in that, also comprises the steps:
(1) incite somebody to action first solution that water simmer down to partly contains nickelous chloride 180g/l,
(2) make that first waste liquid and the volume ratio of first solution are to mix the two at 1.5: 1 to get second waste liquid,
(3) remaining water is adopted after with the hydrogen peroxide deep oxidation second organic extractant carry out the purification by liquid extraction of nickelous chloride in second extraction plant, and through condensing crystal and the nickelous chloride crystal product.
According to the extraction separating method of claim 1 or 10 described Ni from waste etching FeCl 3 solution containing, it is characterized in that 11, second organic extractant is specially 20% N235,10% secondary octanol, 70% kerosene.
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| CN 03131945 CN1211504C (en) | 2003-06-17 | 2003-06-17 | Nickel-containing iron trichloride etching effluent extraction and separation method |
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| CN 03131945 CN1211504C (en) | 2003-06-17 | 2003-06-17 | Nickel-containing iron trichloride etching effluent extraction and separation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554446C (en) * | 2007-09-07 | 2009-10-28 | 金川集团有限公司 | A kind of nickel chloride solution crystalline method |
| CN101497484B (en) * | 2008-01-30 | 2010-11-03 | 深圳市东江环保股份有限公司 | Method for treating ferric trichloride etching waste liquor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534222B (en) * | 2012-01-06 | 2013-12-04 | 南昌大学 | Method for recovering acrylonitrile butadiene styrene (ABS) plastic galvanized parts |
| CN102992513A (en) * | 2012-11-19 | 2013-03-27 | 天津市聚鑫源水处理技术开发有限公司 | Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution |
| CN112661196A (en) * | 2020-12-29 | 2021-04-16 | 斯瑞尔环境科技股份有限公司 | Purification method of ferric trichloride |
| CN113213547A (en) * | 2021-03-10 | 2021-08-06 | 斯瑞尔环境科技股份有限公司 | Method for recovering copper and iron from etching waste liquid |
-
2003
- 2003-06-17 CN CN 03131945 patent/CN1211504C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554446C (en) * | 2007-09-07 | 2009-10-28 | 金川集团有限公司 | A kind of nickel chloride solution crystalline method |
| CN101497484B (en) * | 2008-01-30 | 2010-11-03 | 深圳市东江环保股份有限公司 | Method for treating ferric trichloride etching waste liquor |
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