CN106396195A - Circular treatment method for waste liquid generated by extracting cobalt and nickel by acid leaching process - Google Patents
Circular treatment method for waste liquid generated by extracting cobalt and nickel by acid leaching process Download PDFInfo
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- CN106396195A CN106396195A CN201611067578.4A CN201611067578A CN106396195A CN 106396195 A CN106396195 A CN 106396195A CN 201611067578 A CN201611067578 A CN 201611067578A CN 106396195 A CN106396195 A CN 106396195A
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- magnesium
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- 239000007788 liquid Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims abstract description 35
- 238000002386 leaching Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract 4
- 229910017052 cobalt Inorganic materials 0.000 title abstract 2
- 239000010941 cobalt Substances 0.000 title abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052759 nickel Inorganic materials 0.000 title abstract 2
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 66
- 239000000706 filtrate Substances 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 29
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 22
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 22
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 16
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 16
- 239000003337 fertilizer Substances 0.000 claims abstract description 16
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 14
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 14
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 14
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000000536 complexating effect Effects 0.000 claims abstract description 9
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 9
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008235 industrial water Substances 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 150000001455 metallic ions Chemical class 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 claims 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract 1
- 229910052567 struvite Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920006266 Vinyl film Polymers 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical group [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a circular treatment method of waste liquid generated by extracting cobalt and nickel by an acid leaching process, which comprises the following steps: (1) carrying out precipitation reaction; (2) complexing sodium polyacrylate; (3) carrying out ultrafiltration concentration for the first time; (4) removing obstruction in channels; (5) performing ultrafiltration concentration for the second time; (6) and (5) reverse osmosis concentration and separation. By the treatment method, magnesium in the waste liquid is precipitated by ammonium carbonate and ammonium phosphate to obtain magnesium carbonate and magnesium ammonium phosphate, which are very common magnesium fertilizers, and the effective recycling of magnesium metal is realized. The invention also carries out complexation treatment, two times of ultrafiltration concentration and one time of reverse osmosis concentration treatment on the filtrate obtained after magnesium precipitation, so that the residual metal ions in the filtrate are complexed and separated from the filtrate and are enriched in the metal ion reverse osmosis concentrated solution, the first dialysate and the third dialysate generated in the process can be directly used as the water for production, and the metal ion reverse osmosis concentrated solution can also be used for the steps of acidification and decomplexing, thereby realizing the recycling of the acid liquor.
Description
Technical field
The present invention relates to a kind of method for treating waste liquid is and in particular to a kind of acid leaching process refines following of the produced waste liquid of cobalt nickel
Ring processing method.Belong to metal smelting technical field.
Background technology
Acid leaching process refines the common method of valuable metal, such as, when producing cobalt nickel, directly using acid（Typically sulphur
Acid）The valuable metals such as the cobalt nickel in ore are leached by solution, but, inevitably will be with cobalt nickel association during acidleach
Magnesium, the impurity such as manganese leach in the lump, subsequent leachate is purified and removal of impurities after be settled out cobalt nickel, liquid after the heavy cobalt nickel so obtaining
In contain the impurity such as magnesium, manganese, or even also have cobalt nickel of a small amount of residual etc., simultaneously as employing a large amount of acid in acid leaching process, therefore
Substantial amounts of acid is also contained in produced waste liquid.
It should the waste liquid that said method is produced is further processed in actual production, reach resource recycling
Purpose, it is to avoid waste and the pollution to environment.
Content of the invention
The purpose of the present invention is for overcoming above-mentioned the deficiencies in the prior art, providing a kind of acid leaching process to refine cobalt nickel and produced
The circulation process method of waste liquid.
For achieving the above object, the present invention adopts following technical proposals：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Add sodium hydroxide solution in waste liquid, adjusting pH value is 7～8, add mol ratio to be 1：1～2 ammonium carbonate and phosphorus
Sour ammonium, carries out precipitation reaction and filters, and obtains sediment and filtrate；
（2）Add Sodium Polyacrylate, the residual metallic ion in complexing filtrate in filtrate, form metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time, obtain the first ultrafiltration concentration liquid and the first dislysate, the latter is as industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 1～2, the first ultrafiltration concentration liquid is made by acidifying
In metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration, obtains the second ultrafiltration concentration liquid and the second dislysate, Sodium Polyacrylate
It is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate, obtains metal ion reverse osmosis concentrated liquid and the 3rd dislysate,
The former can be used as step after concentrating lifting acidity further（4）In strong acid liquid recycle；The latter is as industrial water reuse.
Preferably, step（1）Before middle precipitation reaction, first waste liquid is placed in mummifying pool, concentration and evaporation falls 10～20% water
Point, then carry out press filtration using plate and frame filter press, remove 20～25% moisture.
Preferably, step（1）In, the total amount of ammonium carbonate and ammonium phosphate and the mass volume ratio of waste liquid are 1.2～1.8g：
1L, the time of precipitation reaction is 1～2 hour.
Preferably, step（1）In, the mass concentration of sodium hydroxide solution is 40%.
Preferably, step（1）In, sediment is washed with deionized 2～3 times, and is dried 12 under the conditions of 40～80 DEG C
～24 hours, you can obtain the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and ammonium magnesium phosphate）.
Preferably, step（2）In, the Sodium Polyacrylate addition of every liter of filtrate is 1.7～2.1g.
Preferably, step（3）In first time be concentrated by ultrafiltration use milipore filter be molecular cut off 50000 poly- inclined fluorine
Vinyl film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa.
Preferably, step（5）In second ultrafiltration concentration use milipore filter be molecular cut off 50000 poly- inclined fluorine
Vinyl film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa.
Preferably, step（6）In, the process conditions of reverse osmosis concentration are：Pressure 3MPa, feed liquid cycles of concentration is 10 times.
Beneficial effects of the present invention：
Acid leaching process refines and contains a large amount of magnesium produced by cobalt nickel in waste liquid, by the processing method of the present invention, with ammonium carbonate and
Ammonium phosphate precipitates the magnesium in waste liquid, obtains magnesium carbonate and ammonium magnesium phosphate, right and wrong fertiliser containing magnesium usually it is achieved that magnesium metal effective
Recycle.The present invention has also carried out complexing process to the filtrate of gained after precipitation magnesium, two times of ultrafiltration concentrates and a reverse osmosis
Thoroughly concentration so that in filtrate remaining metal ion Separation by Complexation from filtrate out and be enriched in metal ion counter-infiltration
In concentrate, should during produce the first dislysate and the 3rd dislysate can directly as industrial water reuse, and metal from
Sub- reverse osmosis concentrated liquid can be also used for being acidified the step of decomplexing it is achieved that recycling of acid solution.
Specific embodiment
With reference to embodiment the present invention will be further elaborated it should explanation, the description below merely to
Explain the present invention, its content is not defined.
Embodiment 1：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Waste liquid is placed in mummifying pool, concentration and evaporation falls 10% moisture, then carries out press filtration using plate and frame filter press, remove
20% moisture；It is subsequently adding sodium hydroxide solution（40w.t.%）, adjusting pH value is 7, adds mol ratio to be 1：1 ammonium carbonate and
Ammonium phosphate, carries out precipitation reaction 1 hour and filters, obtain sediment and filtrate；Wherein, the total amount of ammonium carbonate and ammonium phosphate and waste liquid
Mass volume ratio be 1.2g：1L, sediment is washed with deionized 2 times, and is dried 12 hours under the conditions of 40 DEG C, you can
To the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and ammonium magnesium phosphate）；
（2）Sodium Polyacrylate is added in filtrate（The Sodium Polyacrylate addition of every liter of filtrate is 1.7g）, in complexing filtrate
Residual metallic ion, forms metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time and separate（The milipore filter using is the polyvinylidene fluoride film of molecular cut off 50000, surpasses
Filtering technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the first ultrafiltration concentration liquid and the first dislysate, Hou Zhezuo
For industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 1, made in the first ultrafiltration concentration liquid by acidifying
Metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration（The milipore filter using is the polyvinylidene fluoride of molecular cut off 50000
Alkene film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the second ultrafiltration concentration liquid and the second dislysate,
Sodium Polyacrylate is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate（Pressure 3MPa, feed liquid cycles of concentration is 10 times）, obtain metal from
Sub- reverse osmosis concentrated liquid and the 3rd dislysate, the former can be used as step after concentrating lifting acidity further（4）In strong acid liquid
Recycle；The latter is as industrial water reuse.
Embodiment 2：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Waste liquid is placed in mummifying pool, concentration and evaporation falls 20% moisture, then carries out press filtration using plate and frame filter press, remove
25% moisture；It is subsequently adding sodium hydroxide solution（40w.t.%）, adjusting pH value is 8, adds mol ratio to be 1：2 ammonium carbonate and
Ammonium phosphate, carries out precipitation reaction 2 hours and filters, obtain sediment and filtrate；Wherein, the total amount of ammonium carbonate and ammonium phosphate and waste liquid
Mass volume ratio be 1.8g：1L, sediment is washed with deionized 3 times, and is dried 24 hours under the conditions of 80 DEG C, you can
To the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and ammonium magnesium phosphate）；
（2）Sodium Polyacrylate is added in filtrate（The Sodium Polyacrylate addition of every liter of filtrate is 2.1g）, in complexing filtrate
Residual metallic ion, forms metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time and separate（The milipore filter using is the polyvinylidene fluoride film of molecular cut off 50000, surpasses
Filtering technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the first ultrafiltration concentration liquid and the first dislysate, Hou Zhezuo
For industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 2, made in the first ultrafiltration concentration liquid by acidifying
Metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration（The milipore filter using is the polyvinylidene fluoride of molecular cut off 50000
Alkene film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the second ultrafiltration concentration liquid and the second dislysate,
Sodium Polyacrylate is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate（Pressure 3MPa, feed liquid cycles of concentration is 10 times）, obtain metal from
Sub- reverse osmosis concentrated liquid and the 3rd dislysate, the former can be used as step after concentrating lifting acidity further（4）In strong acid liquid
Recycle；The latter is as industrial water reuse.
Embodiment 3：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Waste liquid is placed in mummifying pool, concentration and evaporation falls 10% moisture, then carries out press filtration using plate and frame filter press, remove
25% moisture；It is subsequently adding sodium hydroxide solution（40w.t.%）, adjusting pH value is 7, adds mol ratio to be 1：2 ammonium carbonate and
Ammonium phosphate, carries out precipitation reaction 1 hour and filters, obtain sediment and filtrate；Wherein, the total amount of ammonium carbonate and ammonium phosphate and waste liquid
Mass volume ratio be 1.8g：1L, sediment is washed with deionized 2 times, and is dried 12 hours under the conditions of 80 DEG C, you can
To the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and ammonium magnesium phosphate）；
（2）Sodium Polyacrylate is added in filtrate（The Sodium Polyacrylate addition of every liter of filtrate is 2.1g）, in complexing filtrate
Residual metallic ion, forms metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time and separate（The milipore filter using is the polyvinylidene fluoride film of molecular cut off 50000, surpasses
Filtering technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the first ultrafiltration concentration liquid and the first dislysate, Hou Zhezuo
For industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 1, made in the first ultrafiltration concentration liquid by acidifying
Metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration（The milipore filter using is the polyvinylidene fluoride of molecular cut off 50000
Alkene film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the second ultrafiltration concentration liquid and the second dislysate,
Sodium Polyacrylate is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate（Pressure 3MPa, feed liquid cycles of concentration is 10 times）, obtain metal from
Sub- reverse osmosis concentrated liquid and the 3rd dislysate, the former can be used as step after concentrating lifting acidity further（4）In strong acid liquid
Recycle；The latter is as industrial water reuse.
Embodiment 4：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Waste liquid is placed in mummifying pool, concentration and evaporation falls 20% moisture, then carries out press filtration using plate and frame filter press, remove
20% moisture；It is subsequently adding sodium hydroxide solution（40w.t.%）, adjusting pH value is 8, adds mol ratio to be 1：1 ammonium carbonate and
Ammonium phosphate, carries out precipitation reaction 2 hours and filters, obtain sediment and filtrate；Wherein, the total amount of ammonium carbonate and ammonium phosphate and waste liquid
Mass volume ratio be 1.2g：1L, sediment is washed with deionized 3 times, and is dried 24 hours under the conditions of 40 DEG C, you can
To the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and ammonium magnesium phosphate）；
（2）Sodium Polyacrylate is added in filtrate（The Sodium Polyacrylate addition of every liter of filtrate is 1.7g）, in complexing filtrate
Residual metallic ion, forms metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time and separate（The milipore filter using is the polyvinylidene fluoride film of molecular cut off 50000, surpasses
Filtering technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the first ultrafiltration concentration liquid and the first dislysate, Hou Zhezuo
For industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 2, made in the first ultrafiltration concentration liquid by acidifying
Metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration（The milipore filter using is the polyvinylidene fluoride of molecular cut off 50000
Alkene film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the second ultrafiltration concentration liquid and the second dislysate,
Sodium Polyacrylate is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate（Pressure 3MPa, feed liquid cycles of concentration is 10 times）, obtain metal from
Sub- reverse osmosis concentrated liquid and the 3rd dislysate, the former can be used as step after concentrating lifting acidity further（4）In strong acid liquid
Recycle；The latter is as industrial water reuse.
Embodiment 5：
Acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel, including step：
（1）Waste liquid is placed in mummifying pool, concentration and evaporation falls 15% moisture, then carries out press filtration using plate and frame filter press, remove
22% moisture；It is subsequently adding sodium hydroxide solution（40w.t.%）, adjusting pH value is 7, adds mol ratio to be 1：1.5 ammonium carbonate
And ammonium phosphate, carry out precipitation reaction 1.5 hours and filter, obtain sediment and filtrate；Wherein, the total amount of ammonium carbonate and ammonium phosphate with
The mass volume ratio of waste liquid is 1.6g：1L, sediment is washed with deionized 3 times, and dry 18 hours under the conditions of 60 DEG C, that is,
The fertiliser containing magnesium as fertilizer can be obtained（Including magnesium carbonate and ammonium magnesium phosphate）；
（2）Sodium Polyacrylate is added in filtrate（The Sodium Polyacrylate addition of every liter of filtrate is 1.8g）, in complexing filtrate
Residual metallic ion, forms metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time and separate（The milipore filter using is the polyvinylidene fluoride film of molecular cut off 50000, surpasses
Filtering technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the first ultrafiltration concentration liquid and the first dislysate, Hou Zhezuo
For industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 2, made in the first ultrafiltration concentration liquid by acidifying
Metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration（The milipore filter using is the polyvinylidene fluoride of molecular cut off 50000
Alkene film, ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out to press 0.1MPa）, obtain the second ultrafiltration concentration liquid and the second dislysate,
Sodium Polyacrylate is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate（Pressure 3MPa, feed liquid cycles of concentration is 10 times）, obtain metal from
Sub- reverse osmosis concentrated liquid and the 3rd dislysate, the former can be used as step after concentrating lifting acidity further（4）In strong acid liquid
Recycle；The latter is as industrial water reuse.
Test example
Using the metal ion in waste liquid before EDTA compleximetry detection process（Including all metal ions such as magnesium, manganese）Contain
Amount, using the metal ion in waste liquid after atomic absorption spectrography (AAS) detection process（Including all metal ions such as magnesium, manganese）Content,
The results are shown in Table 1.
Table 1. metal ion content situation
As shown in Table 1, after process, waste liquid includes the first dislysate and the 3rd dislysate two parts, and metal ion content therein is equal
＜ 0.023mg/L, meets water quality standard for industries；And, compared with before processing metal ions in waste liquor content, effectively reclaim
Metal ion in waste liquid.
Although the above-mentioned specific embodiment to the present invention is described, not the limit to the scope of the present invention
System, on the basis of technical scheme, those skilled in the art do not need to pay that creative work can make is each
Plant modification or deformation still within protection scope of the present invention.
Claims (9)
1. acid leaching process refines the circulation process method of the produced waste liquid of cobalt nickel it is characterised in that including step：
（1）Add sodium hydroxide solution in waste liquid, adjusting pH value is 7～8, add mol ratio to be 1：1～2 ammonium carbonate and phosphorus
Sour ammonium, carries out precipitation reaction and filters, and obtains sediment and filtrate；
（2）Add Sodium Polyacrylate, the residual metallic ion in complexing filtrate in filtrate, form metal ion complex；
（3）Carry out being concentrated by ultrafiltration for the first time, obtain the first ultrafiltration concentration liquid and the first dislysate, the latter is as industrial water reuse；
（4）It is concentrated by ultrafiltration in liquid to first and adds strong acid liquid, adjust pH value to 1～2, the first ultrafiltration concentration liquid is made by acidifying
In metal ion complex carry out decomplexing；
（5）The solution of decomplexing is carried out second ultrafiltration concentration, obtains the second ultrafiltration concentration liquid and the second dislysate, Sodium Polyacrylate
It is enriched in the second ultrafiltration concentration liquid, and return to step（3）Recycle；
（6）Second dislysate is carried out reverse osmosis concentration separate, obtains metal ion reverse osmosis concentrated liquid and the 3rd dislysate,
The former can be used as step after concentrating lifting acidity further（4）In strong acid liquid recycle；The latter is as industrial water reuse.
2. processing method according to claim 1 is it is characterised in that step（1）Before middle precipitation reaction, first waste liquid is placed in
In mummifying pool, concentration and evaporation falls 10～20% moisture, then carries out press filtration using plate and frame filter press, removes 20～25% water
Point.
3. processing method according to claim 1 is it is characterised in that step（1）In, the total amount of ammonium carbonate and ammonium phosphate with
The mass volume ratio of waste liquid is 1.2～1.8g：1L, the time of precipitation reaction is 1～2 hour.
4. processing method according to claim 1 is it is characterised in that step（1）In, the mass concentration of sodium hydroxide solution
For 40%.
5. processing method according to claim 1 is it is characterised in that step（1）In, sediment is washed with deionized 2
～3 times, and be dried 12～24 hours under the conditions of 40～80 DEG C, you can obtain the fertiliser containing magnesium as fertilizer（Including magnesium carbonate and phosphorus
Sour ammonium magnesium）.
6. processing method according to claim 1 is it is characterised in that step（2）In, the Sodium Polyacrylate of every liter of filtrate adds
Entering amount is 1.7～2.1g.
7. processing method according to claim 1 is it is characterised in that step（3）In first time be concentrated by ultrafiltration use
Milipore filter is the polyvinylidene fluoride film of molecular cut off 50000, and ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out pressure
0.1MPa.
8. processing method according to claim 1 is it is characterised in that step（5）In second ultrafiltration concentration use
Milipore filter is the polyvinylidene fluoride film of molecular cut off 50000, and ultrafiltration technology condition is：Room temperature, enters to press 0.3MPa, goes out pressure
0.1MPa.
9. processing method according to claim 1 is it is characterised in that step（6）In, the process conditions of reverse osmosis concentration
For：Pressure 3MPa, feed liquid cycles of concentration is 10 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109607863A (en) * | 2018-12-26 | 2019-04-12 | 杭州富阳鼎创科技有限公司 | A kind of technique for treating industrial wastewater |
| CN111451004A (en) * | 2020-04-20 | 2020-07-28 | 武汉工程大学 | Method for producing phosphate concentrate and byproducts α -hemihydrate gypsum and magnesium carbonate from calcium collophanite |
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| JP2005305343A (en) * | 2004-04-22 | 2005-11-04 | Tomita Pharmaceutical Co Ltd | Phosphorus recovery method |
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| CN101734815A (en) * | 2009-12-23 | 2010-06-16 | 苏州市环境工程有限责任公司 | Electronic electroplating wastewater recycling advanced treatment technology |
| CN101870461A (en) * | 2010-03-22 | 2010-10-27 | 中国恩菲工程技术有限公司 | Method for treating waste liquid containing magnesium |
| US20120168378A1 (en) * | 2009-09-08 | 2012-07-05 | Toray Industries, Inc | Method for producing pure water and pure water production apparatus |
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| JP2005305343A (en) * | 2004-04-22 | 2005-11-04 | Tomita Pharmaceutical Co Ltd | Phosphorus recovery method |
| CN1899985A (en) * | 2006-07-10 | 2007-01-24 | 三达膜科技（厦门）有限公司 | Treating, recovering and reutilizing method for electroplating waste liquid containing heavy metals |
| US20120168378A1 (en) * | 2009-09-08 | 2012-07-05 | Toray Industries, Inc | Method for producing pure water and pure water production apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109607863A (en) * | 2018-12-26 | 2019-04-12 | 杭州富阳鼎创科技有限公司 | A kind of technique for treating industrial wastewater |
| CN111451004A (en) * | 2020-04-20 | 2020-07-28 | 武汉工程大学 | Method for producing phosphate concentrate and byproducts α -hemihydrate gypsum and magnesium carbonate from calcium collophanite |
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