CN116987905A - Method for recovering heavy metals in electroplating nickel-containing sludge - Google Patents
Method for recovering heavy metals in electroplating nickel-containing sludge Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 43
- 239000010802 sludge Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 36
- 238000009713 electroplating Methods 0.000 title claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000605 extraction Methods 0.000 claims abstract description 44
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 43
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 43
- 239000012074 organic phase Substances 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000004537 pulping Methods 0.000 claims abstract description 4
- 238000007127 saponification reaction Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 69
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 17
- 229910001453 nickel ion Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 ion sulfate Chemical class 0.000 description 1
- 238000005259 measurement Methods 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to the technical field of dangerous waste recovery, and in particular discloses a method for recovering heavy metals in electroplating nickel-containing sludge, which comprises the following steps: s1, drying, grinding and pulping nickel-containing sludge, and then adding 25-35wt% of sulfuric acid: 25-35wt% of hydrogen peroxide is 1: (0.38-0.5) soaking in the mixed solution to obtain filtrate A; s2, adding calcium carbonate into the filtrate A to enable the pH value to be 2.8-3.5, and obtaining filtrate B; s3, adding a saponified P204 extractant into the filtrate B for extraction, and separating to obtain a P204 water phase; s4, adding a saponified P507 extractant into the P204 water phase, and separating to obtain a P507 organic phase; s5, adding the P507 organic phase into sulfuric acid for back extraction, and separating to obtain nickel sulfate-containing liquid; s6, separating oil from the nickel sulfate-containing back extraction liquid, evaporating, concentrating, crystallizing and drying to obtain nickel sulfate, adjusting the process parameters, and having no overflow of hydrogen sulfide and higher metal recovery rate.
Description
Technical Field
The application relates to the technical field of dangerous waste recovery, in particular to a method for recovering heavy metals in electroplating nickel-containing sludge.
Background
At present, about 3 trillions of electroplating plants exist in China, and the processing capacity of the electroplating device is 30 hundred million square meters. However, electroplating plants are small in scale and dispersed, the technology is relatively backward, most of the electroplating plants mainly comprise copper plating, zinc plating, nickel plating and chromium plating, a large amount of solid wastes are produced after electroplating wastewater treatment, and if the wastes are directly buried, the environment is damaged, the human health is endangered, and huge resource waste is caused. The electroplated nickel has the advantages of high uniformity, high wear resistance and the like, so that the electroplated nickel is widely applied to industrial production. The national environmental protection agency has already listed nickel-containing sludge as the seventeenth type of hazardous waste in the national hazardous waste list. Besides the environmental problems caused by dangerous wastes, the recovery of metal elements from waste electroplating sludge not only can recycle resources, but also has certain social and economic benefits.
However, the recovery rate of valuable metals in electroplating sludge is low, so that the recovery is incomplete, the secondary waste is more, and the cost is higher. During acid leaching of nickel sulfide sludge, overflow of hydrogen sulfide is easy to generate, and the requirement on environmental protection facilities is high; and the amount of hydrogen sulfide produced is large, which has adverse effect on the stable operation of environmental protection facilities.
Disclosure of Invention
The application provides a method for recovering heavy metals in electroplating nickel-containing sludge, which aims to reduce overflow of hydrogen sulfide in the process of recovering heavy metals in electroplating sludge and improve metal recovery rate.
The application provides a method for recovering heavy metals in electroplating nickel-containing sludge, which adopts the following technical scheme:
a method for recovering heavy metals in electroplating nickel-containing sludge comprises the following steps:
s1, drying, grinding and pulping nickel-containing sludge, adding 25-35wt% of sulfuric acid and 25-35wt% of hydrogen peroxide, mechanically stirring and acid leaching for 1-2.5 h, and performing filter pressing to obtain filtrate A and filter residue A; the mass ratio of the sulfuric acid to the hydrogen peroxide is 1: (0.38-0.5);
s2, adding calcium carbonate into the filtrate A obtained in the step S1 to adjust the pH to 2.8-3.5, and performing filter pressing to obtain filtrate B and filter residue B;
s3, adding a saponified P204 extractant into the filtrate B obtained in the step S2 for extraction, and separating to obtain a P204 organic phase and a P204 water phase;
s4, adding a saponified P507 extractant into the P204 water phase obtained in the step S3 to extract, and separating to obtain a P507 organic phase and a P507 water phase;
s5, adding the P507 organic phase obtained in the step S4 into sulfuric acid solution for back extraction, and separating to obtain an empty P507 organic phase and nickel sulfate-containing back extraction liquid;
s6, separating oil from the nickel sulfate-containing back extraction liquid obtained in the step S5, evaporating, concentrating, crystallizing and drying to obtain nickel sulfate.
Through adopting above-mentioned technical scheme, after the nickel-containing mud in S1 is through desiccation, crocus, beating, add 30wt% sulfuric acid: 30wt% hydrogen peroxide solution with the mass ratio of 0.38-0.5, and mechanically stirring and soaking for 1-2.5 h to change heavy metal from solid to free state, and filtering to obtain heavy metal ion filtrate 1.
In S2, adding calcium carbonate into the filtrate 1 to adjust the pH to 2.8-3.5, and NiS+H 2 SO 4 +H 2 O 2 →S↓+NiSO 4 +2H 2 O is H in the reaction process 2 S gas escapes according to S 2- Two-step ionization balance of (a) and NiS: (1)K 1 ＝9.1×10-8；②/>K 2 ＝1.1×10-12；③NiS→Ni 2+ +S 2- ，K 3 =1.0×10-24; so long as the reaction (1) does not occur, H will not occur 2 S gas escapes, and the PH is more than 2.5 according to equilibrium constant calculation, namely the reaction (1) does not occur; filtering to obtain heavy metal ion sulfate filtrate 2 and solid sulfur filter residue 2.
S3, adding a P204 extractant into the filtrate 2 obtained in the step S2 for extraction, and separating to obtain a P204 organic phase of copper, zinc, iron and manganese metal ions and a P204 aqueous phase containing nickel; and S4, adding the saponified P507 extractant into the nickel-containing P204 aqueous phase obtained in the step S3, separating to obtain a nickel-containing P507 organic phase and a P507 aqueous phase, and further purifying nickel sulfate. S5, carrying out back extraction on the P507 organic phase obtained in the step S4 by adding sulfuric acid, and separating to obtain an empty P507 organic phase and nickel sulfate-containing back extraction liquid;
and S6, separating oil from the nickel sulfate-containing back extraction liquid obtained in the step S5, evaporating, concentrating, crystallizing and drying to obtain the high-purity nickel sulfate.
As preferable: and the step S3 further comprises the step of adding 2-7mol/L hydrochloric acid solution into the obtained P204 organic phase for back extraction, and separating to obtain an empty P204 organic phase and a back extraction liquid.
By adopting the technical scheme, 2-7mol/L hydrochloric acid is added into the P204 organic phase for back extraction, and the empty P204 organic phase and other ion stripping liquid are separated to obtain the empty P204 organic phase, so that the empty P204 can be recycled, and the recovery rate of copper, zinc, iron and manganese metal ions can be further improved after back extraction.
As preferable: the concentration of sulfuric acid in the step S5 is 2-3mol/L.
By adopting the technical scheme, the concentration of sulfuric acid in the step S5 is controlled to be 2-3mol/L, so that the recovery rate of nickel sulfate can be improved, and the recovery rate of nickel metal ions can be further improved.
As preferable: in the step S3, the P204 extractant is saponified by 20wt% ammonia water or 30wt% liquid alkali, and the saponification rate is 50-60%.
By adopting the technical scheme, the P204 extractant is an acidic organic phosphoric acid extractant, the acidity is weak, the equilibrium is usually reached when the aqueous phase shows slightly acidic reaction, and the extraction quantity is very small. Only the alkali is used for neutralizing the generated acid, so that the extraction amount of the metal can be increased; the metal extraction amount is in direct proportion to the alkali amount of the added ammonia water or liquid alkali, and the proper saponification rate can improve the extraction rate of the metal, so that the saponification rate of the extractant is controlled to be 50-60%, the metal extraction rate can be improved, and the recovery rate of metal ions can be further improved.
As preferable: in the step S4, the P507 extractant is saponified by ammonia water, and the saponification rate is 40-60%.
By adopting the technical scheme, the P507 is an acidic phosphorus extractant, the saponification rate is controlled to be 40-60%, and the recovery rate of nickel metal ions can be further improved.
As preferable: the density of the evaporated, concentrated and crystallized product in the step S6 is 1.55-1.68 kg/m 3 The temperature is 45-55 ℃.
By adopting the technical schemeThe density of the evaporated, concentrated and crystallized product is controlled to be 1.55-1.68 kg/m 3 The temperature is 45-55 ℃, so that the crystal of the nickel sulfate can be grown, and the recovery rate of the nickel sulfate is improved.
As preferable: and in the step S6, the drying temperature is 55-65 ℃ and the time is 1-2 h.
By adopting the technical scheme, the drying temperature in the step S6 is controlled to be 55-65 ℃ and the time is controlled to be 1-2 hours, so that the crystal growth of the nickel sulfate can be uniform, and the recovery rate of the nickel sulfate is improved.
As preferable: the empty P204 organic phase and the empty P507 organic phase can be recycled.
By adopting the technical scheme, the empty P204 organic phase and the empty P507 organic phase obtained by extraction and separation can be recycled, so that the medicament cost can be reduced, and the recovery rate of metal ions can be improved.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) According to the method, the technological parameters in the method for recovering the heavy metal in the nickel-containing sludge by electroplating are regulated, the obtained nickel ion recovery rate, other ion recovery rate and nickel sulfate purity are respectively 97.1%, 92.32% and 98.10%, and no hydrogen sulfide overflows, so that the method has high metal recovery rate.
(2) The application controls the mass ratio of sulfuric acid and hydrogen peroxide, and the recovery rate of nickel ions, the recovery rate of other ions and the purity of nickel sulfate are respectively 83.0-84.8%, 73.85-76.92% and 80.66-82.93%, and no hydrogen sulfide overflows, thereby further improving the recovery rate of metal ions.
(3) The pH value of the filtrate after sludge acid leaching is adjusted to 2.8-3.5, so that the recovery rate of the obtained nickel ions, the recovery rate of other ions and the purity of nickel sulfate are respectively 86.0-86.5%, 78.98-79.81% and 84.45-85.03%, and no hydrogen sulfide overflows, and the recovery rate of metal ions is further improved.
(4) According to the application, the concentration of sulfuric acid is controlled, hydrochloric acid is added into the P204 organic phase obtained after extraction for back extraction, the recovery rate of nickel ions, the recovery rate of other ions and the purity of nickel sulfate are respectively 90.9%, 87.18% and 90.52%, no hydrogen sulfide overflows, and the recovery rate of metal ions is improved.
(5) The application has the advantages that the saponification rate of the P204 extractant is 50-60%, the saponification rate of the P507 extractant is 40-60%, the recovery rate of the obtained nickel ions, the recovery rate of other ions and the purity of nickel sulfate are 94.8%, 92.31% and 94.86%, and no hydrogen sulfide overflows, so that the recovery rate of metal ions is improved.
(6) The application controls the density and temperature of the nickel sulfate evaporation concentration crystallization and the drying temperature, and the recovery rate of the nickel ions, the recovery rate of other ions and the purity of the nickel sulfate are 97.1 percent, 92.32 percent and 98.10 percent respectively, and the recovery rate of nickel metal ions is improved without overflow of hydrogen sulfide.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials in the application are all commercial products, so that the raw materials in the application are fully disclosed, and the raw materials are not to be understood as limiting the sources of the raw materials, and specifically: p204 extractant, active substance content 90%, technical grade; p507 extractant, 95% of effective substance content, and industrial grade.
Example 1
The method for recovering heavy metals in the electroplated nickel-containing sludge of the embodiment 1 comprises the following steps:
s1, drying and grinding nickel-containing sludge, adding water and pulping for 1h, and adding 30wt% sulfuric acid: 30wt% of hydrogen peroxide is 1:0.38, stirring and soaking for 1.5h, and filtering to obtain filtrate A and filter residue A;
s2, adding calcium carbonate into the filtrate A obtained in the step S1 to adjust the pH to 2.8, and filtering to obtain filtrate B and filter residue B;
s3, adding a P204 extractant with a saponification rate of 40% into the filtrate B obtained in the step S2 for extraction, wherein the extraction temperature is 35 ℃, the extraction time is 8min, the volume ratio of the oil phase to the water phase is 2, the stirring rate is 250 r/mm, standing is 30min, and separating to obtain a P204 organic phase and a P204 water phase;
s4, adding a P507 extractant with the saponification rate of 30% into the P204 water phase obtained in the step S3 for extraction, wherein the back extraction temperature is 35 ℃, the volume ratio of the oil phase to the water phase is 1, the stirring rate is 250 r/mm, standing is carried out for 30min, and the P507 organic phase and the P507 water phase are separated;
s5, carrying out back extraction on the P507 organic phase obtained in the step S4 by adding 1.5mol/L sulfuric acid, and separating to obtain an empty P507 organic phase and nickel sulfate-containing back extraction liquid;
s6, feeding the nickel sulfate-containing back extraction solution obtained in the step S5 into an active carbon oil separation tank for oil separation, concentrating and crystallizing by using an Oslo evaporation crystallizer, evaporating the heated solution in an evaporation chamber and supersaturating the heated solution with the density of 1.45kg/m 3 And the solution enters a crystal fluidized bed below the evaporation chamber through a central pipe, supersaturated solute in the solution is deposited on the surfaces of suspended particles in the crystal fluidized bed, and the temperature is controlled at 40 ℃ to enable the crystals to grow. And (3) conveying the uniform crystallized product discharged from the bottom of the fluidized bed to a drying section, and keeping the drying temperature at 50 ℃ for 1.5h to obtain nickel sulfate.
Examples 2 to 3
The method for recovering heavy metals in the nickel-containing sludge by electroplating in examples 2-3 is the same as in example 1, except that the mass ratio of sulfuric acid to hydrogen peroxide in step S1 in examples 2-3 is different, and the other parameters are the same as in example 1, and specific details are shown in Table 1.
Examples 4 to 5
The method for recovering heavy metals in the nickel-containing sludge for electroplating in examples 4 to 5 is the same as in example 2, except that the pH in step S2 is different in examples 4 to 5, and the other parameters are the same as in example 2, and the details are shown in Table 1.
TABLE 1 Process parameter table for recovery method of heavy metals from nickel-containing electroplating sludge
Example 6
The method for recovering heavy metals in the nickel-containing sludge by electroplating in embodiment 6 is the same as in embodiment 4, except that in embodiment 6, step S3 further comprises adding 5mol/L hydrochloric acid solution into the obtained P204 organic phase for back extraction, the extraction temperature is 35 ℃, the extraction time is 8min, the volume ratio of the oil phase to the water phase is 2, the stirring rate is 250 r/mm, standing is 30min, and the empty P204 organic phase and the back extraction liquid are obtained by separation, wherein the rest parameters are the same as in embodiment 4.
Examples 7 to 10
The method for recovering heavy metals in the nickel-containing sludge for electroplating in examples 7-10 is the same as in example 6, except that the sulfuric acid concentration in step S5 in examples 7-10 is different, and the other parameters are the same as in example 6, and the details are shown in Table 2.
TABLE 2 Process parameter Table for recovery method of heavy metals from Nickel-containing electroplating sludge
Example 11
The method for recovering heavy metals from the nickel-plated sludge of example 11 was the same as in example 8, except that the P204 extractant in step S3 of example 11 was saponified with ammonia water, the saponification rate was 55%, and the remaining parameters were the same as in example 8.
Example 12
The method for recovering heavy metals from the nickel-plated sludge of example 12 was the same as in example 11, except that the P507 extractant in step S4 of example 12 was saponified with ammonia water, the saponification rate was 50%, and the remaining parameters were the same as in example 11.
Example 13
The method for recovering heavy metals from the nickel-plated sludge of example 13 is the same as in example 12, except that the density of the evaporated, concentrated crystals in step S6 of example 13 is 1.60kg/m 3 The temperature was 50℃and the remaining parameters were the same as in example 12.
Example 14
The method for recovering heavy metals in the nickel-plated sludge of example 14 is the same as in example 13, except that the drying temperature in step S6 of example 14 is 60℃for 1.5 hours, and the remaining parameters are the same as in example 13.
Comparative examples 1 to 2
The method for recovering heavy metals in the electroplating nickel-containing sludge of comparative examples 1-2 is the same as in example 1, except that the mass ratio of sulfuric acid to hydrogen peroxide in step S1 of comparative examples 1-2 is 0.35 and 0.55, respectively, and the remaining parameters are the same as in example 1.
Comparative examples 3 to 4
The method for recovering heavy metals from the nickel-containing sludge for electroplating of comparative examples 3 to 4 was the same as in example 1, except that the pH in step S2 of comparative examples 3 to 4 was adjusted to 2 and 4, respectively, and the remaining parameters were the same as in example 1.
Performance detection
The purity and recovery rate of nickel and copper, zinc, iron, manganese metal ions obtained in examples 1 to 14 and comparative examples 1 to 2 were examined, and the presence or absence of hydrogen sulfide gas overflow during the experiment was observed, and the examination results are shown in Table 3.
TABLE 3 detection results for examples 1-14 and comparative examples 1-2
The detection results in table 3 show that the recovery rate of nickel ions, the recovery rate of other ions and the purity of nickel sulfate obtained by the recovery method of heavy metal in the electroplating nickel-containing sludge are 97.1%, 92.32% and 98.10%, respectively, and the recovery rate of metal is high without overflow of hydrogen sulfide.
In combination with the various measurements of examples 1-3 and comparative examples 1-2, the nickel ion recovery, other ion recovery, nickel sulfate purity obtained in examples 1-3 were 83.0-84.8%, 73.85-76.92%, and 80.66-82.93%, respectively, and all had no hydrogen sulfide overflow, which was significantly higher than that of comparative examples 1-2, indicating that when 25-35wt% sulfuric acid: 25-35wt% of hydrogen peroxide is 1: (0.38-0.5), and the recovery rate of metal ions is improved. Possibly related to controlling the mass ratio of sulfuric acid and hydrogen peroxide, which can promote the heavy metal to be changed from solid to free state.
In combination with the detection data of examples 4-5 and comparative examples 3-4, the nickel ion recovery rate, other ion recovery rate and nickel sulfate purity obtained in examples 4-5 are 86.0-86.5%, 78.98-79.81% and 84.45-85.03%, respectively, and no hydrogen sulfide overflows, which is higher than that of comparative examples 3-4, and shows that the pH value of the filtrate after sludge acid leaching is adjusted to 2.8-3.5, so that the recovery rate of metal ions is improved. It may be associated with adjusting the pH of the filtrate after acid leaching of the sludge to 2.8-3.5, which may promote the change of heavy metals from solid to free state and reduce hydrogen sulfide overflow.
In examples 4 and 6, the nickel ion recovery rate, the other ion recovery rate and the nickel sulfate purity obtained in example 6 are respectively 87.5%, 86.23% and 86.89%, and no hydrogen sulfide overflows, which is obviously higher than that in example 4, and the recovery rate of metal ions is improved when step S3 further comprises adding 5mol/L hydrochloric acid into the obtained P204 organic phase for back extraction. Possibly, the organic phase P204 obtained in the step S3 is subjected to back extraction, and the recovery of copper, zinc, iron and manganese metal ions can be improved.
In examples 6 and examples 7 to 10, the recovery rate of nickel ions, the recovery rate of other ions and the purity of nickel sulfate obtained in examples 7 to 9 are 88.5 to 90.5%, 87.23 to 89.23% and 87.89 to 89.89%, respectively, and no overflow of hydrogen sulfide occurs, which is obviously higher than that in examples 6 and 10, indicating that the recovery rate of metal ions is improved when the concentration of sulfuric acid in the step S5 is controlled to be 2 to 3mol/L. Possibly related to controlling the concentration of sulfuric acid in the step S5 to be 2-3mol/L, and improving the recovery rate of nickel sulfate.
In examples 8 and 11, the nickel ion recovery rate, other ion recovery rate and nickel sulfate purity obtained in example 11 were 92.5%, 89.74% and 92.41%, respectively, and all had no overflow of hydrogen sulfide, which was significantly higher than in example 8, indicating that the saponification rate was suitable when the P204 extractant was saponified with 20wt% aqueous ammonia or 30wt% aqueous alkali in step S3, and the recovery rate of metal ions was improved. It is possible that the saponification rate of the P204 extractant in the step S3 is 50 to 60% by weight with 20% by weight of ammonia water or 30% by weight of liquid alkali, and the metal extraction rate can be improved.
In examples 11 and 12, the recovery rate of nickel ions, recovery rate of other ions, and purity of nickel sulfate obtained in example 12 were 94.8%, 92.31%, and 94.86%, respectively, and no overflow of hydrogen sulfide was observed, which is significantly higher than in example 8, indicating that the recovery rate of metal ions was improved when the P507 extractant was saponified with aqueous ammonia in step S4, and the saponification rate was 40 to 60%. Possibly, the saponification rate of the P507 extractant in the step S4 is 40 to 60 percent by using ammonia water, and the recovery rate of nickel metal ions can be improved.
In examples 12 and 13, the recovery rate of nickel ions, recovery rate of other ions, purity of nickel sulfate, and purity of nickel sulfate obtained in example 13 were 95.5%, 92.25%, and 96.21%, respectively, and all had no overflow of hydrogen sulfide, which was significantly higher than in example 9, indicating that the density of the evaporated concentrated crystals was 1.55 to 1.68kg/m when the concentration of the evaporated crystals in step S6 was controlled 3 The temperature is proper at 45-55 ℃, and the recovery rate of metal ions is improved. The density of the evaporated, concentrated and crystallized crystals in the possible and control step S6 is 1.55 to 1.68kg/m 3 The temperature is 45-55 ℃, which can promote the crystal growth of the nickel sulfate and improve the recovery rate of the nickel sulfate.
In examples 13 and 14, the nickel ion recovery rate, other ion recovery rate and nickel sulfate purity obtained in example 14 were 97.1%, 92.32% and 98.10%, respectively, and all had no overflow of hydrogen sulfide, which was significantly higher than that in example 10, indicating that the recovery rate of metal ions was improved when the drying temperature was 55-65 ℃ and the time was 1-2 hours in step S6. The method may be related to controlling the drying temperature in the step S6 to be 55-65 ℃ and the time to be 1-2 hours, so that the crystal growth uniformity of the nickel sulfate can be promoted, and the recovery rate of the nickel sulfate can be improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. The method for recovering the heavy metal in the electroplating nickel-containing sludge is characterized by comprising the following steps of:
s1, drying, grinding and pulping nickel-containing sludge, adding 25-35wt% of sulfuric acid and 25-35wt% of hydrogen peroxide, mechanically stirring and acid leaching for 1-2.5 h, and performing filter pressing to obtain filtrate A and filter residue A; the mass ratio of the sulfuric acid to the hydrogen peroxide is 1: (0.38-0.5);
s2, adding calcium carbonate into the filtrate A obtained in the step S1 to adjust the pH to 2.8-3.5, and performing filter pressing to obtain filtrate B and filter residue B;
s3, adding a saponified P204 extractant into the filtrate B obtained in the step S2 for extraction, and separating to obtain a P204 organic phase and a P204 water phase;
s4, adding a saponified P507 extractant into the P204 water phase obtained in the step S3 to extract, and separating to obtain a P507 organic phase and a P507 water phase;
s5, adding the P507 organic phase obtained in the step S4 into sulfuric acid solution for back extraction, and separating to obtain an empty P507 organic phase and nickel sulfate-containing back extraction liquid;
s6, separating oil from the nickel sulfate-containing back extraction liquid obtained in the step S5, evaporating, concentrating, crystallizing and drying to obtain nickel sulfate.
2. The method for recycling heavy metals in nickel-containing sludge in electroplating according to claim 1, wherein the step S3 further comprises adding 2-7mol/L hydrochloric acid solution into the obtained P204 organic phase for back extraction, and separating to obtain an empty P204 organic phase and a back extraction liquid.
3. The method for recovering heavy metals from nickel-containing sludge for electroplating according to claim 1, wherein the concentration of sulfuric acid in the step S5 is 2-3mol/L.
4. The method for recovering heavy metals from nickel-containing sludge by electroplating according to claim 1, wherein the saponification rate of the P204 extractant in the step S3 is 50-60% by using ammonia water or liquid alkali.
5. The method for recovering heavy metals from nickel-containing sludge for electroplating according to claim 1, wherein the P507 extractant in step S4 is saponified with ammonia water, and the saponification rate is 40-60%.
6. The method for recovering heavy metals from nickel-containing sludge for electroplating according to claim 1, wherein the density of the evaporated, concentrated crystals in step S6 is 1.55-1.68 kg/m 3 The temperature is 45-55 ℃.
7. The method for recovering heavy metals from nickel-containing sludge by electroplating according to claim 1, wherein the drying temperature in the step S6 is 55-65 ℃ and the drying time is 1-2 h.
8. The method for recycling heavy metals in nickel-containing sludge for electroplating according to claim 1 or 2, wherein the empty P204 organic phase and the empty P507 organic phase are both recyclable.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge |
| CN101824550A (en) * | 2009-03-02 | 2010-09-08 | 姚龚斌 | Extracting and purifying technology of high purity nickel |
| CN102031373A (en) * | 2009-09-29 | 2011-04-27 | 惠州市东江环保技术有限公司 | Method for recycling nickel and copper from electroplating sludge |
| CN107502757A (en) * | 2017-08-04 | 2017-12-22 | 浙江正道环保科技有限公司 | A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge |
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN114752767A (en) * | 2022-03-10 | 2022-07-15 | 中国恩菲工程技术有限公司 | Method for recovering copper, zinc and nickel from electroplating sludge |
-
2023
- 2023-08-10 CN CN202311002554.0A patent/CN116987905A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004284848A (en) * | 2003-03-20 | 2004-10-14 | Nippon Steel Corp | Method of recovering nickel sulfate from nickel-containing waste water sludge |
| CN101824550A (en) * | 2009-03-02 | 2010-09-08 | 姚龚斌 | Extracting and purifying technology of high purity nickel |
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge |
| CN102031373A (en) * | 2009-09-29 | 2011-04-27 | 惠州市东江环保技术有限公司 | Method for recycling nickel and copper from electroplating sludge |
| CN107502757A (en) * | 2017-08-04 | 2017-12-22 | 浙江正道环保科技有限公司 | A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge |
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN114752767A (en) * | 2022-03-10 | 2022-07-15 | 中国恩菲工程技术有限公司 | Method for recovering copper, zinc and nickel from electroplating sludge |
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