CN104192917A - Nickel-cobalt sulfate continuous-crystallizing process - Google Patents
Nickel-cobalt sulfate continuous-crystallizing process Download PDFInfo
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Abstract
The invention discloses a nickel sulfate hexahydrate crystal and cobalt sulfate heptahydrate crystal continuous-crystallizing process which comprises the following steps: firstly carrying out MVR evaporation concentration on a high-purity solution produced through an extraction procedure to 30%-39%, and secondly continuously cooling and crystallizing through an improved cooling type internal-circulating continuous crystallizer; continuously discharging crystal slurry from the bottom of the crystallizer for centrifugal solid-liquid separation; and continuously drying a crystal product at low temperature to produce product crystals with large granularity and uniform size distribution, and recovering a mother solution to an evaporation process. Compared with the traditional periodic crystallization process, the nickel sulfate hexahydrate crystal and cobalt sulfate heptahydrate crystal continuous-crystallizing process disclosed by the invention has the advantages of low evaporation energy consumption, fewer crystallization control process parameters, stability in operation, high automation degree, high production efficiency and the like and is easy to control, and operators are reduced.
Description
Technical field
The invention belongs to vitriol industrial production technology field, particularly a kind of vitriol continuous crystallisation technique.
Background technology
Industrial production nickel cobalt vitriol be generally dilute solution through single-action, two effects and triple effect evaporation technique be concentrated into saturated after, then carry out single still intermittent cooling crystallization and produce and obtain.There is following shortcoming in this technique: 1, evaporation technology energy consumption is large; 2, crystallisation process control parameter is many, level of automation is low, production efficiency is low, control difficulty is large, personnel qualifications is high.
Summary of the invention
The object of the invention is to overcome the defect existing in prior art, a kind of six hydration nickel sulfate and Cobalt monosulfate heptahydrate continuous crystallisation technique are provided.Mainly comprise the steps:
(1) evaporation concentration: according to the solubility curve of single nickel salt, cobalt sulfate solution, adopt MVR evaporation technology by 15%～25% (wt%) high-purity dilute solution evaporation concentration to 28%～39% of extraction process output, drop temperature is 80～90 ℃, for traditional triple effect evaporation, use MVR evaporation technology can be saved 50～60% standard matchmaker, and energy-saving effect is remarkable;
(2) Continuous Cooling Crystallization: adopt external water cooling type internal recycle continuous crystallizer, control 80～90 ℃ of concentrated solutions of output in step 1 with 1～10m
3the flow of/h enters external water cooler, and external water cooler is connected with crystallizer circulation line, controls the feed liquid internal circulating load 900～1500m of water cooler by recycle pump
3/ h, the mixing speed by variable frequency control crystallizer, at 85～108r/min, makes crystallizer internal recycle amount at 1000～2000m
3in/h flow range, in crystallizer, crystal is in suspended state, and this is conducive to the growth of crystal.Magma temperature in crystallizer is 32～45 ℃, and the temperature of charge of water cooler is higher than 1～5 ℃ of crystallizer magma temperature, and the six hydration nickel sulfate magma that crystallizer bottom discharge mouth is discharged continuously, Cobalt monosulfate heptahydrate magma are to next procedure.For controlling crystal size, crystallizer is provided with thin brilliant cancellation element, dissolves, thereby guarantee growing up of the interior crystal of crystallizer for the supernatant liquor that contains a large amount of fine crystals being returned to evaporization process, and it is 0～3m that supernatant liquor returns liquid measure
3/ h.
(3) filtration drying: the magma of above-mentioned steps 2 outputs is used after whizzer filtering separation, crystal dry obtains that granularity is large, packs after the uniform crystal product of size distribution with vibrated fluidized bed continuous low temperature Wind Volume again, drying temperature is 50～60 ℃, and mother liquor returns to evaporization process.
For water cooler in control above-mentioned steps 2 is because single nickel salt, rose vitriol crystallization scab, affect heat transfer effect, increased the technology and equipment of water cooler recirculated cooling water internal recycling, control the temperature-stable of water cooler heat exchange wall as far as possible, reduce the fluctuation of degree of supersaturation, thereby control the crystal amount of separating out and speed of separating out on water cooler heat exchange wall, recirculated cooling water self-circulation amount is 200～300m
3/ h, recirculated cooling water is respectively 32 ℃ and 38 ℃ to return water temperature.
For controlling vibrated fluidized bed continuous low temperature drying effect in above-mentioned steps 3, avoid uneven drying even, the problems such as crystal reunion, the present invention has increased vibrating material-distributing device before moisture eliminator entrance, the crystal that wets can be scatter uniformly and enter moisture eliminator again on the one hand; Adopt on the other hand vibrating material-distributing device, can also effectively avoid the fragmentation of crystal.
Further, the mass percent of the high-purity sulphuric acid nickel described in step 1, rose vitriol concentrated solution is preferably respectively 30～39%.
Further, in step 2, crystallizer magma and water cooler material temperature difference are preferably 1～3 ℃.
The present invention is for traditional triple effect evaporation, and use MVR evaporation technology can be saved 50～60% standard matchmaker, and energy-saving effect is remarkable, and has realized the serialization production of technique, simple to operation.
Accompanying drawing explanation
Fig. 1: continuous crystallisation process flow sheet
Wherein: 1-crystallizer; 2-water cooler; 3A-coolant circulation pump; 3B-recirculated water self-circulating pump; 4-recirculated water storage tank; 5-valve; 6-valve; 7-valve; 8-valve; 9-valve.
Embodiment
Embodiment 1:
By-pass valve control 7 apertures, 80～90 ℃ of single nickel salt concentrated solutions that solute mass ratio is 37%～39% are with 1～4m
3the flow of/h enters refrigeration cycle pipeline.Control coolant circulation pump P01 variable-frequence governor, adjustment pump flow is 900～1100m
3/ h.By-pass valve control 6 apertures, circulating cooling water flow is 40～85m
3/ h, making water cooler drop temperature is 33～38 ℃.Crystallization control agitator JB01 variable-frequence governor, adjusting and stirring lifting rate is 1000～1200m
3/ h, makes crystal in suspended state, and this classification that is conducive to crystal is grown up, and in crystallizer, magma temperature is 32～35 ℃.Valve 9 is closed.By-pass valve control 5 apertures, the discharging of crystallizer magma is 1～4m
3/ h, and through centrifugal and dry after 75～80% crystal particle diameter at the six hydration nickel sulfate crystal product of 1～2mm.
Embodiment 2:
By-pass valve control 7 apertures, 80～90 ℃ of rose vitriol concentrated solutions that solute mass ratio is 30%～33% are with 4～8m
3the flow of/h enters refrigeration cycle pipeline.Control coolant circulation pump P01 variable-frequence governor, adjustment pump flow is 1100～1250m
3/ h.By-pass valve control 6 apertures, circulating cooling water flow is 80～97m
3/ h, making water cooler drop temperature is 35～40 ℃.Crystallization control agitator JB01 variable-frequence governor, adjusting and stirring lifting rate is 1200～1500m
3/ h, makes crystal in suspended state, and this classification that is conducive to crystal is grown up, and in crystallizer, magma temperature is 32～38 ℃.By-pass valve control 9 apertures, the thin brilliant elimination liquid amount of returning is 1～2m
3/ h.By-pass valve control 5 apertures, the discharging of crystallizer magma is 4～8m
3/ h, and through centrifugal and dry after 80～85% crystal particle diameter at the Cobalt monosulfate heptahydrate crystal product of 1～2mm.
Embodiment 3:
By-pass valve control 7 apertures, 80～90 ℃ of single nickel salt concentrated solutions that solute mass ratio is 38%～39% are with 8～10m
3the flow of/h enters refrigeration cycle pipeline.Control coolant circulation pump P01 variable-frequence governor, adjustment pump flow is 1250～1500m
3/ h.By-pass valve control 6 apertures, circulating cooling water flow is 85～106m
3/ h, making water cooler drop temperature is 39～45 ℃.Crystallization control agitator JB01 variable-frequence governor, adjusting and stirring lifting rate is 1500～1800m
3/ h, makes crystal in suspended state, and in crystallizer, magma temperature is 35～43 ℃.By-pass valve control 9 apertures, the thin brilliant elimination liquid amount of returning is 2～3m
3/ h.By-pass valve control 5 apertures, the discharging of crystallizer magma is 8～10m
3/ h, and through centrifugal and dry after 85～90% crystal particle diameter at the six hydration nickel sulfate product of 1～2mm.
In above-described embodiment, the self-circulation flow 200～300m of recirculated cooling water
3/ h, the cycle of water cooler cleaning during shutdown because heat exchange wall scabs is greater than 3 months.
The foregoing is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, any foundation technical spirit of the present invention is made any simple modification, equivalent variations and modification to above embodiment, all belongs in the scope of technical solution of the present invention.
Claims (6)
1. a nickel cobalt vitriol continuous crystallisation technique, is characterized in that:
(1) 15～25% high-purity sulphuric acid nickel, cobalt sulfate solution are entered to circulation line by MVR technique evaporation concentration to approaching saturated solution, with circulation fluid, enter external water cooler cooling, after described concentrating, approaching saturated solution temperature is 80～90 ℃, and mass percent is 30～39%;
(2) circulation fluid enters crystallizer after cooling by external water cooler again, and water cooler material drop temperature is 32～45 ℃, and crystallizer magma temperature is low 1～5 ℃ than water cooler drop temperature;
(3) magma crystal after centrifuging is packed after continuous low temperature drying, and drying temperature is 50～60 ℃.
2. continuous crystallisation technique as claimed in claim 1, is characterized in that: external water cooler is controlled temperature of charge and degree of supersaturation by the flow of controlled circulation pump and the flow of recirculated cooling water and temperature, and recirculated cooling water self-circulation amount is 200～300m
3/ h, recirculated cooling water is 32 ℃～38 ℃ to return water temperature.
3. continuous crystallisation technique as claimed in claim 1, is characterized in that: crystallizer carrys out controlled circulation amount by controlling the rotating speed of agitator, thereby crystal is suspended.
4. continuous crystallisation technique as claimed in claim 1, it is characterized in that: crystallizer is provided with thin brilliant cancellation element, for the supernatant liquor that contains a large amount of fine crystals being returned to evaporization process, dissolve, thereby guarantee growing up of the interior crystal of crystallizer, it is 0～3m that supernatant liquor returns liquid measure
3/ h.
5. continuous crystallisation technique as claimed in claim 1, is characterized in that: the dry vibrating distributor that adopts, mother liquor returns to evaporization process.
6. technique as claimed in claim 1, is characterized in that: described in step 1, nickel sulfate solution mass percent is preferably 38～39%, and cobalt sulfate solution mass percent is preferably 33～34%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668651A (en) * | 2016-02-03 | 2016-06-15 | 广东佳纳能源科技有限公司 | Production method for cobaltous sulfate heptahydrate |
| CN105776705A (en) * | 2016-04-12 | 2016-07-20 | 衢州华友钴新材料有限公司 | Comprehensive resourceful treatment method for cobalt-nickel smelting wastewater |
| CN107381637A (en) * | 2017-09-04 | 2017-11-24 | 河钢股份有限公司承德分公司 | A kind of method of preventing scaring in ammonium metavanadate crystallization process |
| CN109173329A (en) * | 2018-10-31 | 2019-01-11 | 浙江新和成股份有限公司 | Device for evaporative crystallization |
| CN110665249A (en) * | 2019-10-24 | 2020-01-10 | 昆山三一环保科技有限公司 | MVR high-salinity wastewater crystallization and salt discharge system and process method thereof |
| CN111905398A (en) * | 2020-06-26 | 2020-11-10 | 中国轻工业长沙工程有限公司 | Process for producing nickel cobalt salt and ammonium salt by continuous crystallization |
| US10995014B1 (en) | 2020-07-10 | 2021-05-04 | Northvolt Ab | Process for producing crystallized metal sulfates |
| CN113457200A (en) * | 2021-07-09 | 2021-10-01 | 西安航天华威化工生物工程有限公司 | Accurate path control continuous crystallization system for nickel sulfate |
| CN113476885A (en) * | 2021-07-08 | 2021-10-08 | 斯瑞尔环境科技股份有限公司 | Method for continuously producing iron salt crystals |
| CN114534302A (en) * | 2022-03-21 | 2022-05-27 | 金川集团镍盐有限公司 | Method for continuously cooling and crystallizing nickel sulfate |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668651B (en) * | 2016-02-03 | 2017-03-22 | 广东佳纳能源科技有限公司 | Production method for cobaltous sulfate heptahydrate |
| CN105668651A (en) * | 2016-02-03 | 2016-06-15 | 广东佳纳能源科技有限公司 | Production method for cobaltous sulfate heptahydrate |
| CN105776705A (en) * | 2016-04-12 | 2016-07-20 | 衢州华友钴新材料有限公司 | Comprehensive resourceful treatment method for cobalt-nickel smelting wastewater |
| CN105776705B (en) * | 2016-04-12 | 2018-10-23 | 衢州华友钴新材料有限公司 | A kind of cobalt nickel fibers waste water comprehensive resources treatment method |
| CN107381637A (en) * | 2017-09-04 | 2017-11-24 | 河钢股份有限公司承德分公司 | A kind of method of preventing scaring in ammonium metavanadate crystallization process |
| CN109173329B (en) * | 2018-10-31 | 2023-08-29 | 浙江新和成股份有限公司 | Device for evaporative crystallization |
| CN109173329A (en) * | 2018-10-31 | 2019-01-11 | 浙江新和成股份有限公司 | Device for evaporative crystallization |
| CN110665249A (en) * | 2019-10-24 | 2020-01-10 | 昆山三一环保科技有限公司 | MVR high-salinity wastewater crystallization and salt discharge system and process method thereof |
| CN111905398A (en) * | 2020-06-26 | 2020-11-10 | 中国轻工业长沙工程有限公司 | Process for producing nickel cobalt salt and ammonium salt by continuous crystallization |
| US10995014B1 (en) | 2020-07-10 | 2021-05-04 | Northvolt Ab | Process for producing crystallized metal sulfates |
| CN113476885A (en) * | 2021-07-08 | 2021-10-08 | 斯瑞尔环境科技股份有限公司 | Method for continuously producing iron salt crystals |
| CN113457200A (en) * | 2021-07-09 | 2021-10-01 | 西安航天华威化工生物工程有限公司 | Accurate path control continuous crystallization system for nickel sulfate |
| CN114534302A (en) * | 2022-03-21 | 2022-05-27 | 金川集团镍盐有限公司 | Method for continuously cooling and crystallizing nickel sulfate |
| CN114534302B (en) * | 2022-03-21 | 2023-09-19 | 金川集团镍盐有限公司 | Method for continuously cooling and crystallizing nickel sulfate |
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| CN104192917B (en) | 2017-01-18 |
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