CN114686686B - Three-outlet extraction method and system device for separating nickel salt solution and nickel cobalt solution - Google Patents
Three-outlet extraction method and system device for separating nickel salt solution and nickel cobalt solution Download PDFInfo
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- CN114686686B CN114686686B CN202011643003.9A CN202011643003A CN114686686B CN 114686686 B CN114686686 B CN 114686686B CN 202011643003 A CN202011643003 A CN 202011643003A CN 114686686 B CN114686686 B CN 114686686B
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- 238000000605 extraction Methods 0.000 title claims abstract description 379
- 239000000243 solution Substances 0.000 title claims abstract description 148
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 150000002815 nickel Chemical class 0.000 title claims abstract description 51
- 239000012266 salt solution Substances 0.000 title claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 149
- 150000007524 organic acids Chemical class 0.000 claims abstract description 126
- 239000012074 organic phase Substances 0.000 claims abstract description 104
- 239000007788 liquid Substances 0.000 claims abstract description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002699 waste material Substances 0.000 claims abstract description 56
- LRDDEBYPNRKRRK-UHFFFAOYSA-N [Mg].[Co].[Ni] Chemical compound [Mg].[Co].[Ni] LRDDEBYPNRKRRK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 80
- 238000007127 saponification reaction Methods 0.000 claims description 59
- 239000003599 detergent Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- -1 escape 110 Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 39
- 238000000926 separation method Methods 0.000 abstract description 16
- 150000001868 cobalt Chemical class 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 23
- 229910052749 magnesium Inorganic materials 0.000 description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 19
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LSSAUVYLDMOABJ-UHFFFAOYSA-N [Mg].[Co] Chemical compound [Mg].[Co] LSSAUVYLDMOABJ-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910000976 Electrical steel Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a three-outlet extraction method and a system device for separating and obtaining nickel salt solution and nickel cobalt solution, wherein the method comprises the following steps: and (3) carrying out three-outlet multistage fractional extraction on the nickel-cobalt-magnesium waste liquid by adopting an organic acid extraction solution, respectively obtaining a nickel salt organic phase and a nickel-cobalt organic phase after extraction, and respectively and sequentially carrying out washing and back extraction treatment to obtain a nickel salt solution and a nickel-cobalt solution. The three-outlet extraction method provided by the invention realizes the direct extraction and separation of nickel and cobalt by taking the organic acid extraction solution as the extractant, and the adopted organic acid extraction solution has high extraction rate to nickel and cobalt, thereby effectively solving the problems of long process flow and high investment in the prior art.
Description
Technical Field
The invention belongs to the technical field of extraction and separation, and relates to a three-outlet extraction method and a system device for separating and obtaining nickel salt solution and nickel cobalt solution.
Background
When cobalt concentrate and cobalt intermediate products are used as raw materials to produce cobalt salt (cobalt sulfate and cobalt chloride), cobalt, nickel, magnesium and other impurities are extracted and separated by P507, and raffinate wastewater mainly contains nickel (500-2000 mg/L) and a small amount of cobalt (1-50 mg/L) and other valuable metals; sodium content 50000-60000mg/L and magnesium content 2000-8000 mg/L; while containing a small amount of oil. The traditional process adopts fractional precipitation, the treated wastewater heavy metal ions still have the phenomenon of exceeding standard, the increasingly severe environment-friendly situation can not be satisfied, and the precipitation produces nickel-cobalt-magnesium slag as dangerous waste, so the treatment cost is high. At present, the separation of high-magnesium low-nickel cobalt materials in China mostly adopts a mode of extracting cobalt by P507, extracting magnesium by C272 and extracting nickel by P507 to purify nickel and cobalt, the mode has the defects of long flow, high consumption of raw materials and auxiliary materials, large occupied area of equipment, high investment and the like, and after the two systems are used for a long time, the two systems have the risk of mutual dissolution, so that the extractant is invalid.
CN110438338A discloses a device and method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and combining magnesium oxide, the device comprises a nickel-cobalt separation recovery system, a magnesium combination separation recovery system, an atmosphere roasting furnace and a crusher which are connected in sequence. The method comprises the following steps: firstly, separating and recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid by an extraction method or a vulcanization precipitation method to obtain a magnesium-containing solution; adding bicarbonate and ammonia water into the magnesium-containing solution, stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; drying and roasting basic magnesium carbonate in an atmosphere to obtain high-purity magnesium oxide; and finally crushing the high-purity magnesium oxide to obtain a silicon steel magnesium oxide product. In the method, C272 is used as an extractant for separating nickel and cobalt by an extraction method.
CN111411228A discloses a method for extracting and separating nickel, cobalt and magnesium from nickel-cobalt-magnesium mixed solution, which comprises the following steps: (1) extracting cobalt magnesium; (2) directly washing nickel; (3) two-step magnesium washing; (4) three steps of magnesium washing; and (5) back-extracting cobalt. The method for extracting cobalt and magnesium comprises the following steps: firstly, adding a saponification extractant into a nickel-cobalt-magnesium mixed solution to be treated, controlling the volume ratio of an organic phase to a water phase to be 2:1-1:3, carrying out 3-6-level countercurrent extraction, standing and separating to obtain a high-Co-content high-Mg high-Ni loaded organic phase and a raffinate, and strictly controlling the Co content and the Mg content of the raffinate to be less than 0.1g/L, thereby ensuring that the raffinate is a pure nickel sulfate solution, and the impurity Co content and the Mg content of the raffinate meet the requirements for battery materials. The saponification extractant used is the sodium salt of P507, and the subsequent process for separating nickel cobalt and magnesium is very complicated and is not easy to operate.
CN110438338 discloses a device and a method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and combining magnesium oxide, the device comprises a nickel-cobalt separation recovery system, a magnesium combination separation recovery system, an atmosphere roasting furnace and a crusher which are connected in sequence. The method comprises the following steps: firstly, separating and recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid by an extraction method or a vulcanization precipitation method to obtain a magnesium-containing solution; adding bicarbonate and ammonia water into the magnesium-containing solution, stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; drying and roasting basic magnesium carbonate in an atmosphere to obtain high-purity magnesium oxide; and finally crushing the high-purity magnesium oxide to obtain a silicon steel magnesium oxide product.
However, the existing treatment process of the nickel-cobalt-magnesium waste liquid has long technical flow and high investment cost.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a three-outlet extraction method and a system device for separating and obtaining nickel salt solution and nickel cobalt solution.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a three-outlet extraction method for separating and obtaining a nickel salt solution and a nickel cobalt solution, which is characterized in that the method comprises the following steps: and (3) carrying out three-outlet multistage fractional extraction on the nickel-cobalt-magnesium waste liquid by adopting an organic acid extraction solution, respectively obtaining a nickel salt organic phase and a nickel-cobalt organic phase after extraction, and respectively and sequentially carrying out washing and back extraction treatment to obtain a nickel salt solution and a nickel-cobalt solution.
According to the three-outlet extraction method provided by the invention, the organic acid extraction solution is used as the extractant to realize the direct extraction and separation of nickel and cobalt, the extraction rate of the adopted organic acid extraction solution on nickel and cobalt is high, the cobalt content in the feed liquid can be reduced to 5mg/L by direct extraction, the nickel content is reduced to 5mg/L, the purity of the finally prepared nickel salt and nickel and cobalt mixed salt is high, the purity of the nickel salt and nickel and cobalt mixed salt can reach 99.99%, and the problems of long process flow and high investment in the prior art are effectively solved.
As a preferable technical scheme of the invention, the three-outlet multistage fractional extraction specifically comprises the following steps:
introducing an organic acid extraction solution and nickel cobalt magnesium waste liquid into the extraction tank from the front section and the middle section of the extraction tank respectively, completing primary extraction after mixing the organic acid extraction solution and the nickel cobalt magnesium waste liquid, separating to obtain a water phase and a nickel cobalt organic phase, and discharging the water phase from the front section of the extraction tank;
(II) discharging a part of the nickel-cobalt organic phase from the middle section of the extraction tank, continuously flowing the rest of the nickel-cobalt organic phase to the rear section of the extraction section and mixing with an organic acid extraction solution, allowing cobalt in the nickel-cobalt organic phase to enter the organic acid extraction solution for secondary extraction to obtain a cobalt salt organic phase, and discharging the cobalt salt organic phase from the rear section of the extraction section;
and (III) respectively washing and back-extracting the nickel-cobalt organic phase discharged from the middle section of the extraction tank and the cobalt salt organic phase discharged from the rear section of the extraction tank to obtain a nickel-cobalt solution and a nickel salt solution, and returning the blank organic acid extraction solution obtained after back-extraction to the step (I) for recycling.
As a preferred technical scheme of the invention, in the step (I), the organic acid extraction solution comprises an organic acid extractant and a diluent;
preferably, the volume fraction of the organic acid extractant in the organic acid extraction solution is 5-30%; but are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the flow rate of the organic acid extraction solution in the extraction tank is 1-5L/min; but are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the organic acid extractant comprises one or at least two carboxylic acid extractants;
preferably, the structural general formula of the carboxylic acid extractant is as follows:
wherein 1.ltoreq.n.ltoreq.21, for example 1, 3, 5, 7, 9, 11, 13, 15, 17, 19 or 21, 1.ltoreq.m.ltoreq.21, for example 1, 3, 5, 7, 9, 11, 13, 15, 17, 19 or 21, 10.ltoreq.m+n.ltoreq.22, for example 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, -C n H 2n+1 and-C m H 2m+1 Each independently a straight chain alkyl or branched alkyl group; but are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, n=8, m=6.
Preferably, the diluent comprises one or a combination of at least two of solvent naphtha, kerosene, escaid110, hexane, heptane or dodecane.
As a preferable technical scheme of the invention, in the step (I), the organic acid extraction solution is subjected to saponification treatment before extraction;
the alkali solution concentration used in the saponification treatment is preferably 6 to 14mol/L, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the lye comprises one or a combination of at least two of sodium hydroxide solution, potassium hydroxide solution or ammonia water;
the saponification degree of the organic acid extraction solution is preferably 40 to 60%, and may be, for example, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or 60%, but is not limited to the recited values, and other values not recited in the range are equally applicable.
As a preferable technical scheme of the invention, in the step (III), the washing process adopts a washing agent which is hydrochloric acid or sulfuric acid;
the concentration of the detergent is preferably 0.5 to 2mol/L, and may be, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2.0mol/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the flow rate of the detergent is 0.1 to 0.5L/min, for example, 0.1L/min, 0.15L/min, 0.2L/min, 0.25L/min, 0.3L/min, 0.35L/min, 0.4L/min, 0.45L/min or 0.5L/min, but the flow rate is not limited to the recited values, and other non-recited values within the range are applicable.
Preferably, the stripping agent adopted in the stripping process is sulfuric acid.
Preferably, the flow rate of the stripping agent is 0.05 to 0.5L/min, for example, 0.05L/min, 0.1L/min, 0.15L/min, 0.2L/min, 0.25L/min, 0.3L/min, 0.35L/min, 0.4L/min, 0.45L/min or 0.5L/min, but the stripping agent is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
In a second aspect, the invention provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, the system device comprises an extraction tank, the extraction section is sequentially divided into an extraction front section, an extraction middle section and an extraction back section along the flow direction of organic acid extraction solution, the extraction middle section is sequentially connected with a first washing tank and a first stripping tank along the flow direction of feed liquid, and the extraction back section is sequentially connected with a second washing tank and a second stripping tank along the flow direction of feed liquid.
As a preferable technical scheme of the invention, the extraction front section is provided with an extraction solution inlet and a raffinate outlet.
Preferably, the extraction front section comprises 1-2 extraction sections which are sequentially communicated.
Preferably, the extraction middle section is provided with a feed liquid inlet and a nickel-cobalt organic phase outlet, wherein the feed liquid inlet is close to the extraction front section, and the nickel-cobalt organic phase outlet is far away from the extraction front section.
Preferably, the extraction middle section comprises 1-15 stages of extraction stages which are sequentially connected, for example, 1 stage, 2 stage, 3 stage, 4 stage or 5 stage, but the extraction middle section is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, a nickel salt organic phase outlet is formed in the extraction rear section.
Preferably, the extraction rear section comprises 1-2 extraction sections which are sequentially communicated.
As a preferable technical scheme of the invention, the first washing tank comprises at least one stage of washing section;
preferably, the first washing tank comprises 2-10 stages of washing stages which are sequentially communicated, for example, 2 stages, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages or 10 stages, but the first washing tank is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, along the flow direction of the feed liquid, a feed liquid inlet is formed in a first stage washing section of the first washing tank, a detergent inlet is formed in a last stage washing section, and countercurrent multistage washing is performed on the feed liquid and the detergent in the first washing tank.
Preferably, the first stage washing section of the first washing tank is connected with the extraction rear section, and the waste detergent discharged from the first stage washing section enters the extraction rear section.
Preferably, the first stripping tank comprises at least one stage of stripping section.
Preferably, the first stripping tank comprises 2-5 stages of stripping sections which are sequentially connected, for example, 2 stages, 3 stages, 4 stages or 5 stages, but the first stripping tank is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, along the flow direction of the feed liquid, a feed liquid inlet and a nickel salt outlet are formed in a first stage stripping section of the first stripping tank, a stripping agent inlet and an extraction solution outlet are formed in a last stage stripping section, the feed liquid and the stripping agent are subjected to multistage countercurrent stripping in the first stripping tank, nickel salt solution obtained after stripping is discharged from the nickel salt outlet, and blank organic acid extraction solution is discharged from the extraction solution outlet and returned to the saponification tank.
Preferably, the extraction solution outlet of the first stripping tank is connected to the saponification tank, and the blank organic acid extraction solution discharged from the first stripping tank is returned to the saponification tank for recycling.
As a preferable technical scheme of the invention, the second washing tank comprises at least one stage of washing section;
preferably, the second washing tank comprises 2-10 stages of washing stages which are sequentially communicated, for example, 2 stages, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages or 10 stages, but the second washing tank is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, along the flow direction of the feed liquid, a feed liquid inlet is formed in a first stage washing section of the second washing tank, a detergent inlet is formed in a last stage washing section, and countercurrent multistage washing is performed on the feed liquid and the detergent in the second washing tank.
Preferably, the first stage washing section of the second washing tank is connected with the extraction front section, and the waste detergent discharged from the first stage washing section enters the extraction front section.
Preferably, the second stripping tank comprises at least one stage of stripping section.
Preferably, the second stripping tank comprises 2-5 stages of stripping sections which are sequentially connected, for example, 2 stages, 3 stages, 4 stages or 5 stages, but the second stripping tank is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Preferably, along the flow direction of the feed liquid, a feed liquid inlet and a nickel cobalt outlet are formed in a first stage stripping section of the second stripping tank, a stripping agent inlet is formed in a last stage stripping section, the feed liquid and the stripping agent are subjected to multistage countercurrent stripping in the second stripping tank, and nickel cobalt solution obtained after stripping is discharged from the nickel cobalt outlet.
As a preferred embodiment of the present invention, the system device further comprises a saponification tank connected to the extraction front section.
Preferably, the saponification tank comprises at least one primary saponification section.
Preferably, the saponification tank comprises 1-4 stages of saponification stages which are sequentially communicated, for example, 1 stage, 2 stage, 3 stage or 4 stage, but the saponification tank is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The system refers to an equipment system, a device system or a production device.
Compared with the prior art, the invention has the beneficial effects that:
according to the three-outlet extraction method provided by the invention, the organic acid extraction solution is used as the extractant to realize the direct extraction and separation of nickel and cobalt, the extraction rate of the adopted organic acid extraction solution on nickel and cobalt is high, the cobalt content in the feed liquid can be reduced to 5mg/L by direct extraction, the nickel content is reduced to 5mg/L, the purity of the finally prepared nickel salt and nickel and cobalt mixed salt is high, the purity of the nickel salt and nickel and cobalt mixed salt can reach 99.99%, and the problems of long process flow and high investment in the prior art are effectively solved.
Drawings
Fig. 1 is a schematic structural diagram of a three-outlet extraction system device according to an embodiment of the present invention.
Wherein, 1-saponification groove; 2-an extraction tank; 21-extraction front section; 22-extracting a middle section; 23-extracting a rear section; 3-a first washing tank; 4-a first stripping tank; 5-a second washing tank; 6-a second stripping tank.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus are not to be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
It should be noted that, in the description of the present invention, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
It will be appreciated by those skilled in the art that the present invention necessarily includes the necessary piping, conventional valves and general pumping equipment for achieving the process integrity, but the foregoing is not a major inventive aspect of the present invention, and that the present invention is not particularly limited thereto as the layout may be added by themselves based on the process flow and the equipment configuration options.
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
In a specific embodiment, the invention provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, which is shown in fig. 1, and comprises an extraction tank 2, wherein the extraction tank 2 is sequentially divided into an extraction front section 21, an extraction middle section 22 and an extraction rear section 23 along the flow direction of organic acid extraction solution, the extraction middle section 22 is sequentially connected with a first washing tank 3 and a first stripping tank 4 along the flow direction of feed liquid, and the extraction rear section 23 is sequentially connected with a second washing tank 5 and a second stripping tank 6 along the flow direction of feed liquid.
The extraction front section 21 is provided with an extraction solution inlet and a raffinate outlet, and the extraction front section 21 comprises 1-2 extraction sections which are sequentially communicated. The extraction middle section 22 is provided with a feed liquid inlet and a nickel-cobalt organic phase outlet, wherein the feed liquid inlet is close to the extraction front section 21, the nickel-cobalt organic phase outlet is far away from the extraction front section 21, and the extraction middle section 22 comprises 1-15 extraction sections which are sequentially communicated. The extraction rear section 23 is provided with a nickel salt organic phase outlet, and the extraction rear section 23 comprises 1-2 extraction sections which are sequentially communicated.
The first washing tank 3 comprises at least one stage of washing section, and further, the first washing tank 3 comprises 2-10 stages of washing sections which are communicated in sequence. Along the flow direction of the feed liquid, a feed liquid inlet is formed in a first stage washing section of the first washing tank 3, a detergent inlet is formed in a last stage washing section, and countercurrent multistage washing is performed between the feed liquid and the detergent in the first washing tank 3. The first-stage washing section of the first washing tank 3 is connected with the extraction rear section 23, and waste washing agent discharged from the first-stage washing section enters the extraction rear section 23.
The first stripping tank 4 comprises at least one stage of stripping section, and further, the first stripping tank 4 comprises 2-5 stages of stripping sections which are communicated in sequence. Along the flow direction of the feed liquid, a feed liquid inlet and a nickel salt outlet are formed in a first stage stripping section of the first stripping tank 4, a stripping agent inlet and an extraction solution outlet are formed in a last stage stripping section, the feed liquid and the stripping agent are subjected to multistage countercurrent stripping in the first stripping tank 4, nickel salt solution obtained after stripping is discharged from the nickel salt outlet, and blank organic acid extraction solution is discharged from the extraction solution outlet. The extraction solution outlet of the first stripping tank 4 is connected into the saponification tank 1, and the blank organic acid extraction solution discharged from the first stripping tank 4 is returned into the saponification tank 1 for recycling.
The second washing tank 5 comprises at least one stage of washing section, and further, the second washing tank 5 comprises 2-10 stages of washing sections which are communicated in sequence. Along the flow direction of the feed liquid, a feed liquid inlet is formed in a first stage washing section of the second washing tank 5, a detergent inlet is formed in a last stage washing section, and countercurrent multistage washing is performed between the feed liquid and the detergent in the second washing tank 5. The first-stage washing section of the second washing tank 5 is connected with the extraction front section 21, and the waste washing agent discharged from the first-stage washing section enters the extraction front section 21.
The second stripping tank 6 comprises at least one stage of stripping section, and further, the second stripping tank 6 comprises 2-5 stages of stripping sections which are communicated in sequence. Along the flow direction of the feed liquid, a feed liquid inlet and a nickel cobalt outlet are formed in a first stage stripping section of the second stripping tank 6, a stripping agent inlet is formed in a final stage stripping section, the feed liquid and the stripping agent are subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel cobalt solution obtained after stripping is discharged from the nickel cobalt outlet.
The system device also comprises a saponification groove 1 connected with the extraction front section 21, wherein the saponification groove 1 comprises at least one grade of saponification section, and further, the saponification groove 1 comprises 1-4 grades of saponification sections which are sequentially communicated.
In another embodiment, the invention provides a system device for three-outlet extraction separation of nickel-cobalt-magnesium waste liquid, which is provided by the embodiment, and the specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 5-30%; introducing the organic acid extraction solution and 6-14 mol/L alkali liquor into a saponification tank 1 to carry out multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 40-60%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=3, m=7, -C 3 H 7 and-C 7 H 15 Are all straight-chain alkyl groups;
(2) The saponified organic acid extraction solution and nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow rate of the organic acid extraction solution in the extraction tank 2 is 1-5L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase is subjected to multistage countercurrent washing in the second washing tank 5 by hydrochloric acid or sulfuric acid with the concentration of 0.5-2 mol/L, the flow rate of the hydrochloric acid or sulfuric acid in the second washing tank 5 is 0.1-0.5L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.05-0.5L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, hydrochloric acid or sulfuric acid with the concentration of 0.5-2 mol/L is subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the hydrochloric acid or sulfuric acid in the first washing tank 3 is 0.1-0.5L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of the organic phase being 0.05-0.5L/min, and nickel salt solution and blank organic acid extraction solution are obtained after stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Example 1
The embodiment provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, wherein, saponification groove 1 includes 1 level saponification section, extraction anterior segment includes 1 level extraction section, extraction middle section includes 1 level extraction section, extraction posterior segment includes 1 level extraction section, first washing tank includes the 2 level washing sections that communicate in proper order, the second washing tank includes the 2 level washing sections that communicate in proper order, first stripping tank includes the 2 level stripping section that communicates in proper order, the second stripping tank includes the 2 level stripping section that communicates in proper order.
The embodiment also provides a method for extracting and separating the nickel-cobalt-magnesium waste liquid by adopting the three-outlet extraction system device, wherein the content of magnesium in the nickel-cobalt-magnesium waste liquid to be treated is 14g/L, the content of nickel is 2.1g/L, the content of cobalt is 0.5g/L, and the flow rate of the nickel-cobalt-magnesium waste liquid is 10L/min.
The specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 15%; introducing the organic acid extraction solution and 10mol/L sodium hydroxide solution into a saponification tank 1 to carry out multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 50%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=5, m=8, -C 5 H 11 and-C 8 H 17 Are branched alkyl groups;
(2) The saponified organic acid extraction solution and the nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow rate of the organic acid extraction solution in the extraction tank 2 is 1.5L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the second washing tank 5, the flow speed of the sulfuric acid in the second washing tank 5 is 0.3L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.2L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, the cobalt salt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the sulfuric acid in the first washing tank 3 is 0.3L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of 0.2L/min, and a nickel salt solution and a blank organic acid extraction solution are obtained after the stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Example 2
The embodiment provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, the three-outlet extraction system device based on concrete implementation provides, wherein, saponification groove 1 is including the 2 level saponification sections that communicate in proper order, the extraction anterior segment includes 1 level extraction section, the extraction middle section includes 4 level extraction sections (feed liquid entry has been seted up to the 1 st level of extraction middle section, nickel cobalt organic phase export has been seted up to the 2 nd level of extraction middle section), the extraction posterior segment includes 1 level extraction section, first washing tank includes the 4 level washing sections that communicate in proper order, the second washing tank includes the 4 level washing sections that communicate in proper order, first back extraction tank includes the 3 level back extraction sections that communicate in proper order, the second back extraction tank includes the 3 level back extraction sections that communicate in proper order.
The embodiment also provides a method for extracting and separating the nickel-cobalt-magnesium waste liquid by adopting the three-outlet extraction system device, wherein the content of magnesium in the nickel-cobalt-magnesium waste liquid to be treated is 11g/L, the content of nickel is 1.4g/L, the content of cobalt is 0.4g/L, and the flow rate of the nickel-cobalt-magnesium waste liquid is 8L/min.
The specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 20%; introducing the organic acid extraction solution and 8mol/L sodium hydroxide solution into a saponification tank for multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 45%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=8, m=6, -C 8 H 17 Is a straight-chain alkyl, -C 6 H 13 Is a branched alkyl group.
(2) The saponified organic acid extraction solution and nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow rate of the organic acid extraction solution in the extraction tank 2 is 3L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the second washing tank 5, the flow speed of the sulfuric acid in the second washing tank 5 is 0.5L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.3L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, the cobalt salt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the sulfuric acid in the first washing tank 3 is 0.5L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of 0.3L/min, and a nickel salt solution and a blank organic acid extraction solution are obtained after the stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Example 3
The embodiment provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, the three-outlet extraction system device based on concrete implementation provides, wherein, saponification groove 1 is including the 3 level saponification sections that communicate in proper order, the extraction anterior segment includes 2 level extraction sections, the extraction middle section includes 8 level extraction sections (feed liquid entry has been seted up to the 1 st level of extraction middle section, nickel cobalt organic phase export has been seted up to the 3 rd level of extraction middle section), the extraction posterior segment includes 2 level extraction sections, first washing tank includes the 6 level washing sections that communicate in proper order, the second washing tank includes the 6 level washing sections that communicate in proper order, first back extraction tank includes the 4 level back extraction sections that communicate in proper order, the second back extraction tank includes the 4 level back extraction sections that communicate in proper order.
The embodiment also provides a method for extracting and separating the nickel-cobalt-magnesium waste liquid by adopting the three-outlet extraction system device, wherein the content of magnesium in the nickel-cobalt-magnesium waste liquid to be treated is 11g/L, the content of nickel is 1.4g/L, the content of cobalt is 0.4g/L, and the flow rate of the nickel-cobalt-magnesium waste liquid is 10L/min.
The specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 25%; introducing the organic acid extraction solution and 12mol/L sodium hydroxide solution into a saponification tank 1 to carry out multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 55%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=10, m=8, -C 10 H 21 and-C 8 H 17 Are all straight-chain alkyl groups;
(2) The saponified organic acid extraction solution and the nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow rate of the organic acid extraction solution in the extraction tank 2 is 2.5L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the second washing tank 5, the flow speed of the sulfuric acid in the second washing tank 5 is 0.16L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.09L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, the cobalt salt organic phase and sulfuric acid with the concentration of 1mol/L are subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the sulfuric acid in the first washing tank 3 is 0.16L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of 0.09L/min, and a nickel salt solution and a blank organic acid extraction solution are obtained after the stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Example 4
The embodiment provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, the three-outlet extraction system device based on concrete implementation provides, wherein, saponification groove 1 is including 4 grades of saponification sections that communicate in proper order, the extraction anterior segment includes 2 grades of extraction sections, the extraction middle section includes 12 grades of extraction sections (feed liquid entry has been seted up to the 1 st grade of extraction middle section, nickel cobalt organic phase export has been seted up to the 4 th grade of extraction middle section), the extraction posterior segment includes 2 grades of extraction sections, first washing tank includes 8 grades of washing sections that communicate in proper order, the second washing tank includes 8 grades of washing sections that communicate in proper order, first back extraction tank includes 5 grades of back extraction sections that communicate in proper order, the second back extraction tank includes 5 grades of back extraction sections that communicate in proper order.
The embodiment also provides a method for extracting and separating the nickel-cobalt-magnesium waste liquid by adopting the three-outlet extraction system device, wherein the content of magnesium in the nickel-cobalt-magnesium waste liquid to be treated is 11g/L, the content of nickel is 1.4g/L, the content of cobalt is 0.4g/L, and the flow rate of the nickel-cobalt-magnesium waste liquid is 10L/min.
The specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 5%; introducing the organic acid extraction solution and a 6mol/L sodium hydroxide solution into a saponification tank 1 to carry out multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 40%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=12, m=8, -C 12 H 25 and-C 8 H 17 Are branched alkyl groups;
(2) The saponified organic acid extraction solution and nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow rate of the organic acid extraction solution in the extraction tank 2 is 1L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase and sulfuric acid with the concentration of 0.5mol/L are subjected to multistage countercurrent washing in the second washing tank 5, the flow speed of the sulfuric acid in the second washing tank 5 is 0.1L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.05L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, the cobalt salt organic phase and sulfuric acid with the concentration of 0.5mol/L are subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the sulfuric acid in the first washing tank 3 is 0.1L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of 0.05L/min, and a nickel salt solution and a blank organic acid extraction solution are obtained after the stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Example 5
The embodiment provides a three-outlet extraction system device for separating and obtaining nickel salt solution and nickel cobalt solution, the three-outlet extraction system device is based on concrete implementation, wherein, saponification groove 1 includes 4 grades of saponification sections that communicate in proper order, the extraction anterior segment includes 2 grades of extraction sections, the extraction middle section includes 15 grades of extraction sections (feed liquid entry has been seted up to the 1 st grade of extraction middle section, nickel cobalt organic phase export has been seted up to the 5 th grade of extraction middle section), the extraction posterior segment includes 2 grades of extraction sections, first washing tank includes 10 grades of washing sections that communicate in proper order, second washing tank includes 10 grades of washing sections that communicate in proper order, first back extraction tank includes 5 grades of back extraction sections that communicate in proper order, second back extraction tank includes 5 grades of back extraction sections that communicate in proper order.
The embodiment also provides a method for extracting and separating the nickel-cobalt-magnesium waste liquid by adopting the three-outlet extraction system device, wherein the content of magnesium in the nickel-cobalt-magnesium waste liquid to be treated is 14g/L, the content of nickel is 2.1g/L, the content of cobalt is 0.5g/L, and the flow rate of the nickel-cobalt-magnesium waste liquid is 10L/min.
The specific operation process comprises the following steps:
(1) Mixing an organic acid extractant and a diluent to obtain an organic acid extraction solution, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 30%; introducing the organic acid extraction solution and 14mol/L sodium hydroxide solution into a saponification tank 1 to carry out multistage concurrent saponification to obtain an organic acid extraction solution with a saponification degree of 60%; the chemical formula of the organic acid extractant is shown in the following formula:
wherein n=8, m=6, -C 8 H 17 and-C 6 H 13 Are all straight-chain alkyl groups;
(2) The saponified organic acid extraction solution and nickel cobalt magnesium waste liquid are respectively introduced into an extraction tank 2 from an extraction front section 21 and an extraction middle section 22, the flow speed of the organic acid extraction solution in the extraction tank 2 is 5L/min, the organic acid extraction solution and the nickel cobalt magnesium waste liquid are mixed and then are extracted for one time, a water phase and a nickel cobalt organic phase are obtained by separation, and the water phase is discharged from the extraction front section 21;
(3) A part of the nickel-cobalt organic phase is discharged from the extraction middle section 22, the rest of the nickel-cobalt organic phase sequentially flows to the extraction rear section 23 and is mixed with the organic acid extraction solution, cobalt in the nickel-cobalt organic phase enters the organic acid extraction solution to finish secondary extraction to obtain a cobalt salt organic phase, and the cobalt salt organic phase is discharged from the extraction rear section 23;
(4) The nickel-cobalt organic phase discharged from the extraction middle section 22 enters a second washing tank 5, the nickel-cobalt organic phase and sulfuric acid with the concentration of 2mol/L are subjected to multistage countercurrent washing in the second washing tank 5, the flow speed of the sulfuric acid in the second washing tank 5 is 0.4L/min, and waste detergent generated after washing is returned to the extraction front section 21; the washed nickel-cobalt organic phase enters a second stripping tank 6, the sulfuric acid with the flow rate of 0.5L/min is subjected to multistage countercurrent stripping in the second stripping tank 6, and nickel-cobalt solution is obtained after stripping and is discharged;
(5) In the step (4), the cobalt salt organic phase discharged from the extraction rear section 23 enters the first washing tank 3, the cobalt salt organic phase and sulfuric acid with the concentration of 2mol/L are subjected to multistage countercurrent washing in the first washing tank 3, the flow speed of the sulfuric acid in the first washing tank 3 is 0.4L/min, and waste detergent generated after washing is returned to the extraction rear section 23; the washed nickel salt organic phase enters a first stripping tank 4, the nickel is subjected to multistage countercurrent stripping in the first stripping tank 4 along the sulfuric acid with the flow rate of 0.5L/min, and a nickel salt solution and a blank organic acid extraction solution are obtained after the stripping, wherein the nickel salt solution is discharged, and the blank organic acid extraction solution is returned to the saponification tank 1 for recycling.
Comparative example 1
This comparative example differs from example 3 in that the organic acid extractant used in step (I) was replaced with P507, and the remaining process parameters and operating steps were exactly the same as in example 3.
Comparative example 2
This comparative example differs from example 3 in that the organic acid extractant used in step (I) was replaced with P507, and the remaining process parameters and operating steps were exactly the same as in example 3.
The nickel content and cobalt content in the aqueous phase (mainly magnesium sulfate) discharged in step (2) were measured in examples 1 to 5 and comparative examples 1 to 2, and the purity of nickel cobalt sulfate discharged in the second stripping tank 6 and nickel sulfate discharged in the first stripping tank 4 were measured, and the results are shown in table 1.
TABLE 1
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (17)
1. A three-outlet extraction method for separating and obtaining nickel salt solution and nickel cobalt solution, which is characterized by comprising the following steps:
introducing an organic acid extraction solution and nickel cobalt magnesium waste liquid into the extraction tank from the front section and the middle section of the extraction tank respectively, completing primary extraction after mixing the organic acid extraction solution and the nickel cobalt magnesium waste liquid, separating to obtain a water phase and a nickel cobalt organic phase, and discharging the water phase from the front section of the extraction tank;
(II) discharging a part of the nickel-cobalt organic phase from the middle section of the extraction tank, continuously flowing the rest of the nickel-cobalt organic phase to the rear section of the extraction section and mixing with an organic acid extraction solution, and allowing nickel in the nickel-cobalt organic phase to enter the organic acid extraction solution to finish secondary extraction to obtain a nickel salt organic phase, wherein the nickel salt organic phase is discharged from the rear section of the extraction section;
and (III) respectively washing and back-extracting the nickel-cobalt organic phase discharged from the middle section of the extraction tank and the nickel-salt organic phase discharged from the rear section of the extraction tank to obtain a nickel-cobalt solution and a nickel-salt solution, and returning the blank organic acid extraction solution obtained after back-extraction to the step (I) for recycling.
2. The three-outlet extraction process of claim 1, wherein in step (i), the organic acid extraction solution comprises an organic acid extractant and a diluent.
3. The three-outlet extraction method according to claim 2, wherein the volume fraction of the organic acid extractant in the organic acid extraction solution is 5-30%.
4. The three-outlet extraction method according to claim 2, wherein the flow rate of the organic acid extraction solution in the extraction tank is 1-5L/min.
5. The three-outlet extraction process of claim 2, wherein the organic acid extractant comprises one or at least two carboxylic acid extractants.
6. The three-outlet extraction method according to claim 5, wherein the carboxylic acid extractant has the following structural formula:
wherein n is not less than 1 and not more than 21, m is not less than 1 and not more than 21, m+n is not less than 10 and not more than 22, -C n H 2n+1 and-C m H 2m+1 Each independently is a straight chain alkyl or a branched alkyl.
7. The three-outlet extraction process of claim 6, wherein n=8, m=6.
8. The three-outlet extraction process of claim 2, wherein the diluent comprises one or a combination of at least two of solvent naphtha, kerosene, escape 110, hexane, heptane, or dodecane.
9. The three-outlet extraction process of claim 1, wherein in step (i), the organic acid extraction solution is subjected to saponification prior to extraction.
10. The three-outlet extraction method according to claim 9, wherein the saponification treatment uses an alkali solution concentration of 6 to 14mol/L.
11. The three-outlet extraction process of claim 10, wherein the lye comprises one or a combination of at least two of sodium hydroxide solution, potassium hydroxide solution, or aqueous ammonia.
12. The three-outlet extraction method according to claim 9, wherein the saponification degree of the organic acid extraction solution is 40-60%.
13. The three-outlet extraction method according to claim 1, wherein in the step (iii), the washing process uses a washing agent of hydrochloric acid or sulfuric acid.
14. The three-outlet extraction method according to claim 13, wherein the concentration of the detergent is 0.5 to 2mol/L.
15. The three-outlet extraction method according to claim 13, wherein the flow rate of the detergent is 0.1 to 0.5L/min.
16. The three-outlet extraction method according to claim 1, wherein in the step (iii), the stripping agent used in the stripping process is sulfuric acid.
17. The three-outlet extraction method according to claim 16, wherein the flow rate of the stripping agent is 0.05-0.5L/min.
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| CN111304460A (en) * | 2018-12-12 | 2020-06-19 | 格林美（江苏）钴业股份有限公司 | Method for extracting and separating cobalt and nickel from nickel-cobalt high-acid leaching solution |
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| AU2005209332A1 (en) * | 2004-01-28 | 2005-08-11 | Commonwealth Scientific And Industrial Research Organisation | Solvent extraction process for separating cobalt and/or nickel from impurities in leach solutions. |
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