CN106745340B - The method of heavy metal nickel is recycled from high fluorine-containing electrolysis fused salt - Google Patents
The method of heavy metal nickel is recycled from high fluorine-containing electrolysis fused salt Download PDFInfo
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- CN106745340B CN106745340B CN201611266451.5A CN201611266451A CN106745340B CN 106745340 B CN106745340 B CN 106745340B CN 201611266451 A CN201611266451 A CN 201611266451A CN 106745340 B CN106745340 B CN 106745340B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention relates to a kind of methods of the high fluorine-containing electrolysis fused salt of recycling, and in particular to a method of heavy metal nickel is recycled from high fluorine-containing electrolysis fused salt.The method of the present invention that heavy metal nickel is recycled from high fluorine-containing electrolysis fused salt, includes the following steps: that (1) crushes: high fluorine-containing electrolysis fused salt being crushed, sieving, obtain high fluorine-containing electrolysis fused salt powder；(2) wash, separate: after cleaning solution washing is added in high fluorine-containing electrolysis fused salt powder, centrifuge separation obtains filtrate and filter residue；(3) it roasts: filter residue being roasted, metal nickel oxide is obtained.The present invention is using high fluorine-containing electrolysis fused salt as raw material, using broken-washing, separation-roasting method, carries out resource utilization to the heavy metal nickel in high fluorine-containing electrolysis fused salt, and the oxide of metallic nickel is made；Process flow is succinct, and the rate of recovery of metallic nickel is 95% or more；Ammonia nitrogen is effectively removed, secondary pollution is avoided；Using roasting technique, without the auxiliary materials such as soda acid, non-wastewater discharge；It recycles and does not contain fluorine ion in product.
Description
Technical field
The present invention relates to a kind of methods of the high fluorine-containing electrolysis fused salt of recycling, and in particular to a kind of from high fluorine-containing electrolysis fused salt
The method for recycling heavy metal nickel.
Background technique
Tungsten hexafluoride is the fluoride materials of current tungsten.Tungsten hexafluoride is industrially for example borontrifluoride with metal tungsten powder and fluorization agent
Nitrogen or fluorine nitrogen are bound up.Fluorization agent in electrolysis by can uniquely be stabilized and by the kind of industrialized production, main use
In electronics industry chemical vapor deposition (CVD) technique raw material, WSi is made with it2When can be used as large scale integrated circuit (LSI)
Prepared by the method for wiring, with the progress of electrolytic process, anode nickel plates gradually use up and generate deposition, and unreacted with part
Material co-deposition forms fused salt in bottom of electrolytic tank, and main component is the metals and its fluorinated inorganic salt etc. such as nickel, iron.
If high fluorine-containing electrolysis fused salt is not recycled, production cost not only will increase, but also environment will be polluted.To electricity
Solve fused salt metallic nickel recycling, also have pertinent literature report, i.e., the recovery method mainly used be by electrolysis fused salt washing,
It digests and precipitates under strongly alkaline conditions, the method extracted and prepare nickel compound.The digestion, removing impurity by means of precipitation matter technical process will
A large amount of entrainment metallic nickel ions, greatly reduce the rate of recovery of nickel；And the sewage of a large amount of higher COD contents is generated, it brings secondary
Pollution.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide one kind recycles heavy metal from high fluorine-containing electrolysis fused salt
The method of nickel, process flow is succinct, and production cost is low, and nickel recovery is high；It effectively removes ammonia nitrogen, avoid secondary pollution；It obtains
Metallic nickel oxide content height, not fluoride ion.
The method of the present invention that heavy metal nickel is recycled from high fluorine-containing electrolysis fused salt, includes the following steps:
(1) it crushes: high fluorine-containing electrolysis fused salt being crushed, sieving, obtain high fluorine-containing electrolysis fused salt powder；
(2) wash, separate: after cleaning solution washing is added in high fluorine-containing electrolysis fused salt powder, centrifuge separation obtains filtrate and filter
Slag；
(3) it roasts: filter residue being roasted, metal nickel oxide is obtained.
Wherein:
The mass content of fluorine element is 30% or more in the fluorine-containing electrolysis fused salt of the height.
The fluorine-containing electrolysis fused salt of height is the fluorine-containing electrolysis fused salt containing nickel, iron, ammonium salt etc..
The grit number of crossing is 20~400 mesh.
Preferably, the grit number of crossing is 100~200 mesh.
The washing is that the concentration of washing to fluorine ion is lower than 0.1g/L.
The cleaning solution is water and/or the filtrate that is centrifugally separating to obtain, high fluorine-containing electrolysis fused salt powder and cleaning solution
Mass ratio is 1:0.3~2.
The washing is dissolution agitator treating or spray washing, and wash temperature is 50~95 DEG C, dissolves agitator treating
Mixing time is 0.5~3 hour.
The centrifuge separation temperature is 50~95 DEG C.
The maturing temperature is 500~900 DEG C, and calcining time is 1~6 hour.
Preferably, the maturing temperature is 650~750 DEG C, and calcining time is 2~3 hours.
In conclusion beneficial effects of the present invention are as follows:
1, the present invention is using high fluorine-containing electrolysis fused salt as raw material, using broken-washing, separation-roasting method, to high fluorine-containing
The heavy metal nickel being electrolysed in fused salt carries out resource utilization, and the oxide of metallic nickel is made.Process flow is succinct, production cost
Low, the rate of recovery of metallic nickel is 95% or more.
2, the filtrate being centrifugally separating to obtain is crystallized, ammonium acid fluoride can be recycled simultaneously, effectively remove ammonia nitrogen, avoided
Secondary pollution.
3, fluorine ion is not contained in present invention recycling product.
4, the present invention uses roasting technique, without the auxiliary materials such as soda acid, non-wastewater discharge.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Raw material used in the examples is commercially available.
Embodiment 1
1000g is electrolysed for fused salt, and sample composition and content are as follows:
| Component | Ni | Fe | Cu | NH4 + | F- | H+ | It is other |
| Content/% | 33.6 | 1.5 | 0.2 | 16.3 | 47.0 | 0.9 | 0.5 |
It is as follows from the method for wherein recycling heavy metal nickel:
Step 1 crushes: being crushed using crusher to high fluorine-containing electrolysis fused salt, smashed fused salt sieving, sieving
20 mesh of mesh number.
Step 2, washing, separation: the powder and water that the first step is obtained are mixed according to the ratio ingredient of 1:1, in 60 DEG C of items
It stirs 3 hours under part, and is separated at 55 DEG C, respectively obtain filtrate and filter residue.
Roasting: step 3 roasts 6 hours for 600 DEG C of filter residue obtained by step 2, obtains metal nickel oxide 439g, product testing
It the results are shown in Table 1.
1 testing result of table
| Component | Nickel oxide | Iron oxide | Copper oxide | Fluorine element |
| Content/% | 94.8 | 4.6 | 0.6 | It is not detected |
| Nickel recovery/% | 97.2 | -- | -- | -- |
Embodiment 2
1000g is electrolysed for fused salt, and sample composition and content are as follows:
| Component | Ni | Fe | Cu | NH4 + | F- | H+ | It is other |
| Content/% | 42.7 | 1.8 | 0.3 | 12.2 | 41.8 | 1.2 | 0.3 |
It is as follows from the method for wherein recycling heavy metal nickel:
Step 1 crushes: being crushed using crusher to high fluorine-containing electrolysis fused salt, smashed fused salt sieving, sieving
200 mesh of mesh number.
Step 2, washing, separation: the circulation fluid ingredient of the powder that the first step is obtained and 1 deal mixes, in 95 DEG C of conditions
Lower stirring 1 hour, and separated at 85 DEG C, respectively obtain filtrate and filter residue；Take the circulation fluid spray washing of 95 DEG C of 1 deal above-mentioned again
Filter residue, separating filtrate and filter residue at 85 DEG C.
Step 3, roasting: 900 DEG C of filter residue of step 2 final gained roasts 3 hours, obtains 561 grams of metal nickel oxide, product
Testing result is shown in Table 2.
2 testing result of table
| Component | Nickel oxide | Iron oxide | Copper oxide | Fluorine element |
| Content/% | 95.7 | 3.8 | 0.5 | It is not detected |
| Nickel recovery/% | 98.9 | -- | -- | -- |
Embodiment 3
1000g is electrolysed for fused salt, and sample composition and content are as follows:
| Component | Ni | Fe | NH4 + | F- | H+ | It is other |
| Content/% | 35.1 | 1.5 | 14.5 | 47.5 | 1.0 | 0.4 |
It is as follows from the method for wherein recycling heavy metal nickel:
Step 1 crushes: being crushed using crusher to high fluorine-containing electrolysis fused salt, smashed fused salt sieving, sieving
350 mesh of mesh number.
Step 2, washing, separation: the circulation fluid ingredient of the powder that the first step is obtained and 1 deal mixes, in 95 DEG C of conditions
Lower stirring 1 hour, and separated at 75 DEG C, respectively obtain filtrate and filter residue；The water spray of 75 DEG C of 0.5 deal is taken to wash above-mentioned filter again
Slag, separating filtrate and filter residue at 75 DEG C.
Step 3, roasting: 750 DEG C of filter residue of step 2 final gained roasts 1 hour, obtains 443 grams of metal nickel oxide, product
Testing result is shown in Table 3.
3 testing result of table
| Component | Nickel oxide | Iron oxide | Fluorine element |
| Content/% | 96.0 | 4.0 | It is not detected |
| The rate of recovery/% | 95.4 | -- | -- |
Claims (7)
1. a kind of method for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, characterized by the following steps:
(1) it crushes: high fluorine-containing electrolysis fused salt being crushed, sieving, obtain high fluorine-containing electrolysis fused salt powder；
(2) wash, separate: after cleaning solution washing is added in high fluorine-containing electrolysis fused salt powder, centrifuge separation obtains filtrate and filter residue,
The filtrate being centrifugally separating to obtain is crystallized；
(3) it roasts: filter residue being roasted, metal nickel oxide is obtained；
The described fluorine-containing electrolysis fused salt of height be containing nickel, iron, ammonium salt fluorine-containing electrolysis fused salt；In the fluorine-containing electrolysis fused salt of height
The mass content of fluorine element is 30% or more；
The cleaning solution is water and/or the filtrate being centrifugally separating to obtain, the quality of high fluorine-containing electrolysis fused salt powder and cleaning solution
Than for 1:0.3~2；
The washing is dissolution agitator treating or spray washing, and wash temperature is 50~95 DEG C, dissolves the stirring of agitator treating
Time is 0.5~3 hour.
2. the method according to claim 1 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Cross grit number be 20~400 mesh.
3. the method according to claim 2 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Cross grit number be 100~200 mesh.
4. the method according to claim 1 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Washing be washing to fluorine ion concentration lower than 0.1g/L.
5. the method according to claim 1 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Centrifuge separation temperature be 50~95 DEG C.
6. the method according to claim 1 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Maturing temperature be 500~900 DEG C, calcining time be 1~6 hour.
7. the method according to claim 6 for recycling heavy metal nickel from high fluorine-containing electrolysis fused salt, it is characterised in that: described
Maturing temperature be 650~750 DEG C, calcining time be 2~3 hours.
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| CN1074946A (en) * | 1992-01-31 | 1993-08-04 | 孟宇 | Refine the processing method of nickel oxide from the aluminium scrap nickel alloy powder |
| CN1167832A (en) * | 1996-02-13 | 1997-12-17 | 三德金属工业株式会社 | Method for recovering reusable elements from rare earth-nickel alloy |
| CN1495295A (en) * | 2002-01-30 | 2004-05-12 | 江西南方稀土高技术股份有限公司 | Method for removing fluorinl and removing dust from waste gas produced by fused salt electrolysis of rare earth metal in fluorination system |
| CN104843761A (en) * | 2015-03-31 | 2015-08-19 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost |
| CN105256156A (en) * | 2015-10-27 | 2016-01-20 | 赣南师范学院 | Process for decomposing fluorine-containing rare earth molten salt waste residues |
| CN105350028A (en) * | 2015-11-24 | 2016-02-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Nitinol powder prepared through molten salt electrolysis and preparing method of nitinol powder |
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- 2016-12-31 CN CN201611266451.5A patent/CN106745340B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| CN1074946A (en) * | 1992-01-31 | 1993-08-04 | 孟宇 | Refine the processing method of nickel oxide from the aluminium scrap nickel alloy powder |
| CN1167832A (en) * | 1996-02-13 | 1997-12-17 | 三德金属工业株式会社 | Method for recovering reusable elements from rare earth-nickel alloy |
| CN1495295A (en) * | 2002-01-30 | 2004-05-12 | 江西南方稀土高技术股份有限公司 | Method for removing fluorinl and removing dust from waste gas produced by fused salt electrolysis of rare earth metal in fluorination system |
| CN104843761A (en) * | 2015-03-31 | 2015-08-19 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost |
| CN105256156A (en) * | 2015-10-27 | 2016-01-20 | 赣南师范学院 | Process for decomposing fluorine-containing rare earth molten salt waste residues |
| CN105350028A (en) * | 2015-11-24 | 2016-02-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Nitinol powder prepared through molten salt electrolysis and preparing method of nitinol powder |
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| 双氧水氢化废镍催化剂回收利用的研究;王玉强;《当代化工》;20060430;第35卷(第2期);第90-92页 * |
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Effective date of registration: 20190820 Address after: 256300 No. 5, No. 4 Road, Gaoqing Chemical Industrial Park, Gaocheng Town, Gaoqing County, Zibo City, Shandong Province Patentee after: Shandong Feiyuan Gas Co.,Ltd. Address before: 256300 Qinghe Industrial Park, Gaoqing County, Shandong, Zibo Patentee before: SHANDONG FEIYUAN TECHNOLOGY Co.,Ltd. |
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Address after: No.5, No.4 Road, Gaoqing Chemical Industrial Park, Gaocheng Town, Gaoqing County, Zibo City, Shandong Province, 256300 Patentee after: Nanda Optoelectronics (Zibo) Co.,Ltd. Address before: No.5, No.4 Road, Gaoqing Chemical Industrial Park, Gaocheng Town, Gaoqing County, Zibo City, Shandong Province, 256300 Patentee before: Shandong Feiyuan Gas Co.,Ltd. |
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