CN102642963A - Comprehensive treatment method of salt-contained waste water produced by extracting vanadium from stone coal - Google Patents
Comprehensive treatment method of salt-contained waste water produced by extracting vanadium from stone coal Download PDFInfo
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- CN102642963A CN102642963A CN2012101103133A CN201210110313A CN102642963A CN 102642963 A CN102642963 A CN 102642963A CN 2012101103133 A CN2012101103133 A CN 2012101103133A CN 201210110313 A CN201210110313 A CN 201210110313A CN 102642963 A CN102642963 A CN 102642963A
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Abstract
The invention relates to a comprehensive treatment method of salt-contained waste water produced by extracting vanadium from stone coal. The invention adopts the technical scheme that: firstly pre-treating the salt-contained waste water until the following conditions are satisfied: iron ion (Fe<2+>) is less than 0.3mg/L, manganese ion (Mn<2+>) is less than 0.1mg/L, and SS is less than 1mg/L; carrying out desalting treatment by utilizing reversed-electrode electrodialysis, concentrating the salt-contained waste water to 100000 to 120000mg/L, and recycling fresh water for a stone-coal vanadium extraction process; carrying out the concentration treatment by adopting a vacuum membrane distillation way, acquiring saturated salt water and condensed water, recycling the condensed water for the stone-coal vanadium extraction process, and feeding the saturated salt water into a concentrated water pool; finally carrying out the crystallization in a crystallization chamber which is previously filled with sodium chloride (NaCl), drying the crystallized salt in the sun to acquire the industrial salt, and returning the acquired industrial salt to the stone-coal vanadium extraction process; and filtering and returning the crystallization liquid to the concentrated water pool to be returned to the vacuum membrane distillation process after being mixed and heated with the concentrated water produced by the electrodialysis. According to the comprehensive treatment method, the energy consumption is small, fresh water and salt in the waste water can be completely recycled, comprehensive utilization of the waste water is realized, no secondary pollution occurs to the environment, and the treatment cost is low.
Description
Technical field
The invention belongs to brine waste and handle and the comprehensive utilization field, relate in particular to a kind of integrated conduct method of extracting vanadium from stone coal brine waste.
Background technology
Along with vanadium in extensive applications such as iron and steel, chemical industry, aerospace, the consumption of vanadium constantly increases.China is as one of abundant country of vanadium resource, become gradually vanadium market, the world strong rival (Wang Yongshuan etc., China's extracting vanadium from stone coal and comprehensive utilization summary " vanadium titanium " 1993,4:21-31).Bone coal is a kind of important vanadium resource that contains of China, has big, the characteristics such as extensive that distribute of reserves, and therefore vanadium extraction is to satisfy the important channel of vanadium demand from now on from bone coal.In the stone coal vanadium-extracting roasting process, need to add certain amount of industrial salt promotes vanadium as roasting additive extraction usually; Very high (the Yi-Min Zhang of saltiness that causes vanadium extracting waste water; Et al.The technology of extracting Vanadium from stone coal in China:History; Current status and future prospects. " Hydrometallurgy " 2011,109:116～124).This brine waste can etching apparatus, if not treatedly directly efflux, can cause the soil compaction of discharge areas, and farm crop are impaired, water body salinization, influence ecological environment.So, must handle this type of brine waste, realize the comprehensive utilization of waste water simultaneously, reduce production costs.
Brine waste is carried out desalting treatment, and the harmless emission of realizing such water body is one of current environmental protection field urgent problem.Current; Generally adopt metallic reducing-lime neutralisation to handle for the extracting vanadium from stone coal brine waste, this method technical process is simple, can remove most of deleterious heavy metal ion (Ceng Fanyong in the waste water; " engineering design and research (Changsha) " 1996 is inquired in the wastewater treatment of acid system extracting vanadium from stone coal; 3:62-64), but still there is the salt concn problem of higher in the waste water after handling, needs further to handle.
When the technology of pre-treatment brine waste has multi-effect distilling and membrane method treating process: multi-effect distilling can concentrate saline solns dramatically; But because the service temperature of waste water is near 100 ℃, energy expenditure is very big, the perishable (Yu Kailu etc. of equipment; Low temperature multiple-effect distillation sea water desalting engineering and technical progress " Chinese water supply and drainage " 2008; 24:82-85), exist facility investment huge simultaneously, the very high shortcoming of processing cost; Membrane method treating process has r-o-and electrodialysis, owing to need not waste water is heated to comparatively high temps in the treating processes, has reduced energy consumption; But membrane method treating process is had relatively high expectations to pre-treatment, and film pollutes easily, and (Chu Yanjie etc., reverse osmosis membrane pollute and in face distribution characteristics research " water technology " 2012; 38:72-74; 133), owing to receive the restriction of film properties, concentrating degree is limited simultaneously; And high strong brine discharging (Zhao Shigang etc., discussion " process water and waste water that reverse osmosis concentrated water is recycled of some secondary still after handling; Li Guang etc., the development of electrodialytic technique and application " chemical technology and exploitation " 2008 37:28-30), can cause second environmental pollution.
Summary of the invention
The present invention is intended to overcome the defective of prior art, purpose provides that a kind of energy expenditure is less, processing cost is lower, to the environment non-secondary pollution, can all reclaim the wherein integrated conduct method of the extracting vanadium from stone coal brine waste of fresh water and salt.
For realizing above-mentioned purpose, the concrete steps of the technical scheme that the present invention adopts are:
The first step, pre-treatment
Adopt lime neutralization-soda ash to remove hard-flocculent precipitation, with the pre-treatment of extracting vanadium from stone coal brine waste extremely: Fe
2+＜0.3mg/L, Mn
2+＜0.1mg/L, SS＜1mg/L.
Second step, pole-reversing electroosmosis
Adopt pole-reversing electroosmosis that pretreated extracting vanadium from stone coal brine waste is carried out desalting treatment; Per 2～2.5 hours reverses once in the desalting treatment process; Extracting vanadium from stone coal brine waste salinity after pole-reversing electroosmosis is handled is concentrated into 100000～120000mg/L; Obtain fresh water and dense water, wherein fresh water is back to process for extracting vanadium from stone coal.
The 3rd step, pressure reducing film distillation
The dense water that adopts pressure reducing film distillation technology that second step was obtained carries out concentration, and per-meate side vacuum tightness is 90～95kPa in the concentration process, obtains saturated brine and water of condensation, and water of condensation is back to process for extracting vanadium from stone coal, and saturated brine gets into dense pond.
The 4th step, crystallization
Crystallization be with crystallisation chamber that dense pond communicates in carry out, be added with solid NaCl in the crystallisation chamber in advance; The saturated brine that gets into crystallisation chamber from dense pond is in the crystallisation chamber crystallization, and the crystal salt after the crystallization makes Industrial Salt through evaporating brine, and the gained Industrial Salt returns process for extracting vanadium from stone coal; Crystal solution is returned dense pond through filtration, the dense hydration that the supernatant in dense pond and electrodialysis are produced also, the supernatant after the merging and dense water return the 3rd pressure reducing film distillation technology that goes on foot after heating.
Total salinity of said extracting vanadium from stone coal brine waste is 10000～35000mg/L.
The thermal source of said heating is an industrial waste heat, and heated temperatures is 55～75 ℃.
Used membrane distillation assembly adopts tubular fibre formula membrane module in the described pressure reducing film distillation, and the filling ratio of tubular fibre formula membrane module is 30%～60%, and length-to-diameter ratio is (3～6): 1; The material of tubular fibre formula membrane module is hydrophobicity pvdf or hydrophobicity tetrafluoroethylene, and mean pore size is 0.2 μ m.
Because adopt technique scheme, heating thermal source of the present invention is an industrial waste heat, and only need the extracting vanadium from stone coal brine waste is heated to 55～75 ℃, when the preparation Industrial Salt, adopt the technology of evaporating brine, so energy expenditure is less; In the comprehensive treating process process, can all reclaim wherein fresh water and salt, the final product direct reuse has been realized the comprehensive utilization of waste water in process for extracting vanadium from stone coal, and to the environment non-secondary pollution, processing cost is low.
The present invention also has the technology flexible characteristic, both can be used for the comprehensive treating process of extracting vanadium from stone coal brine waste, also can be used for other industry and goes up the processing of brine waste, brackish water desalination processing and sea water desaltination processing.
Description of drawings
Fig. 1 is a kind of process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention being further described, is not the restriction to its protection domain:
For avoiding repetition, the chemical ingredients that earlier this embodiment institute will be carried out the extracting vanadium from stone coal brine waste of comprehensive treating process is described below, and repeat no more among the embodiment: always salinity is 10000～35000mg/L, Ca
2+Be 300～650mg/L, Mg
2+Be 60～300mg/L, SS (suspended solid) is 400～750mg/L; Main heavy metal ion is: Zn
2+Be 45～75mg/L, Fe
2+Be 30～50mg/L, Cu
2+Be 10～30mg/L, Mn
2+Be 0.5～4mg/L.
Embodiment 1
A kind of integrated conduct method of extracting vanadium from stone coal brine waste.The concrete steps of its treatment process are as shown in Figure 1:
The first step, pre-treatment
Adopt lime neutralization-soda ash to remove hard-flocculent precipitation, with the pre-treatment of extracting vanadium from stone coal brine waste extremely: Fe
2+＜0.3mg/L, Mn
2+＜0.1mg/L, SS＜1mg/L.
Second step, pole-reversing electroosmosis
Adopt pole-reversing electroosmosis that pretreated extracting vanadium from stone coal brine waste is carried out desalting treatment; Per 2～2.5 hours reverses once in the desalting treatment process; Extracting vanadium from stone coal brine waste salinity after pole-reversing electroosmosis is handled is concentrated into 100000～110000mg/L; Obtain fresh water and dense water, wherein fresh water is back to process for extracting vanadium from stone coal.
The 3rd step, pressure reducing film distillation
The dense water that adopts pressure reducing film distillation technology that second step was obtained carries out concentration, and per-meate side vacuum tightness is 90～95kPa in the concentration process, obtains saturated brine and water of condensation, and water of condensation is back to process for extracting vanadium from stone coal, and saturated brine gets into dense pond.
The 4th step, crystallization
Crystallization be with crystallisation chamber that dense pond communicates in carry out, be added with solid NaCl in the crystallisation chamber in advance; The saturated brine that gets into crystallisation chamber from dense pond is in the crystallisation chamber crystallization, and the crystal salt after the crystallization makes Industrial Salt through evaporating brine, and the gained Industrial Salt returns process for extracting vanadium from stone coal; Crystal solution is returned dense pond through filtration, the dense hydration that the supernatant in dense pond and electrodialysis are produced also, the supernatant after the merging and dense water return the 3rd pressure reducing film distillation technology that goes on foot after heating.
The thermal source of the said heating of present embodiment is an industrial waste heat, and heated temperatures is 55～65 ℃.
Used membrane distillation assembly adopts tubular fibre formula membrane module in the described pressure reducing film distillation of present embodiment, and the filling ratio of tubular fibre formula membrane module is 30%～40%, and length-to-diameter ratio is (3～4): 1; The material of tubular fibre formula membrane module is the hydrophobicity pvdf, and mean pore size is 0.2 μ m.
Embodiment 2
A kind of integrated conduct method of extracting vanadium from stone coal brine waste.The concrete steps of its treatment process are as shown in Figure 1
The first step, pre-treatment
With embodiment 1 the first step.
Second step, pole-reversing electroosmosis
Adopt pole-reversing electroosmosis that pretreated extracting vanadium from stone coal brine waste is carried out desalting treatment; Per 2～2.5 hours reverses once in the desalting treatment process; Extracting vanadium from stone coal brine waste salinity after pole-reversing electroosmosis is handled is concentrated into 110000～120000mg/L; Obtain fresh water and dense water, wherein fresh water is back to process for extracting vanadium from stone coal.
The 3rd step, pressure reducing film distillation
With the 3rd step of embodiment 1.
The 4th step, crystallization
Except that heated temperatures is 65～75 ℃, all the other are with the 4th step of embodiment 1.
Used membrane distillation assembly adopts tubular fibre formula membrane module in the described pressure reducing film distillation of present embodiment, and the filling ratio of tubular fibre formula membrane module is 40%～60%, and length-to-diameter ratio is (4～6): 1; The material of tubular fibre formula membrane module is the hydrophobicity tetrafluoroethylene, and mean pore size is 0.2 μ m.
The heating thermal source of this embodiment is an industrial waste heat, and only needs the extracting vanadium from stone coal brine waste is heated to 55～75 ℃, when the preparation Industrial Salt, adopts the technology of evaporating brine, so energy expenditure is less; In treating processes, can all reclaim fresh water and salt wherein, the final product direct reuse has been realized the comprehensive utilization of waste water in process for extracting vanadium from stone coal, and to the environment non-secondary pollution, processing cost is low.
This embodiment also has the technology flexible characteristic, both can be used for the comprehensive treating process of extracting vanadium from stone coal brine waste, also can be used for other industry and goes up the processing of brine waste, brackish water desalination processing and sea water desaltination processing.
Claims (4)
1. the integrated conduct method of an extracting vanadium from stone coal brine waste is characterized in that the step of said integrated conduct method is:
The first step, pre-treatment
Adopt lime neutralization-soda ash to remove hard-flocculent precipitation, with the pre-treatment of extracting vanadium from stone coal brine waste extremely: Fe
2+＜0.3mg/L, Mn
2+＜0.1mg/L, SS＜1mg/L;
Second step, pole-reversing electroosmosis
Adopt pole-reversing electroosmosis that pretreated extracting vanadium from stone coal brine waste is carried out desalting treatment; Per 2～2.5 hours reverses once in the desalting treatment process; Extracting vanadium from stone coal brine waste salinity after pole-reversing electroosmosis is handled is concentrated into 100000～120000mg/L; Obtain fresh water and dense water, wherein fresh water is back to process for extracting vanadium from stone coal;
The 3rd step, pressure reducing film distillation
The dense water that adopts pressure reducing film distillation technology that second step was obtained carries out concentration, and per-meate side vacuum tightness is 90～95kPa in the concentration process, obtains saturated brine and water of condensation, and water of condensation is back to process for extracting vanadium from stone coal, and saturated brine gets into dense pond;
The 4th step, crystallization
Crystallization be with crystallisation chamber that dense pond communicates in carry out, be added with solid NaCl in the crystallisation chamber in advance; The saturated brine that gets into crystallisation chamber from dense pond is in the crystallisation chamber crystallization, and the crystal salt after the crystallization makes Industrial Salt through evaporating brine, and the gained Industrial Salt returns process for extracting vanadium from stone coal; Crystal solution after the crystallization is returned dense pond through filtration, the dense hydration that the supernatant in dense pond and electrodialysis are produced also, the supernatant after the merging and dense water return the 3rd pressure reducing film distillation technology that goes on foot after heating.
2. the integrated conduct method of extracting vanadium from stone coal brine waste according to claim 1, the total salinity that it is characterized in that said extracting vanadium from stone coal brine waste is 10000～35000mg/L.
3. the integrated conduct method of extracting vanadium from stone coal brine waste according to claim 1, the thermal source that it is characterized in that said heating is an industrial waste heat, heated temperatures is 55～75 ℃.
4. the integrated conduct method of extracting vanadium from stone coal brine waste according to claim 1; It is characterized in that membrane distillation assembly used in the described pressure reducing film distillation adopts tubular fibre formula membrane module; The filling ratio of tubular fibre formula membrane module is 30%～60%, and length-to-diameter ratio is (3～6): 1; The material of tubular fibre formula membrane module is the hydrophobicity pvdf or is the hydrophobicity tetrafluoroethylene that mean pore size is 0.2 μ m.
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| CN108609775A (en) * | 2018-05-25 | 2018-10-02 | 北京林业大学 | A kind of method of efficient process waste incineration leachate reverse osmosis concentrated water |
| CN115020757A (en) * | 2022-06-09 | 2022-09-06 | 四川星明能源环保科技有限公司 | Electrodialysis-based method for removing organic matters in strong acid vanadium solution |
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| CN108609775A (en) * | 2018-05-25 | 2018-10-02 | 北京林业大学 | A kind of method of efficient process waste incineration leachate reverse osmosis concentrated water |
| CN115020757A (en) * | 2022-06-09 | 2022-09-06 | 四川星明能源环保科技有限公司 | Electrodialysis-based method for removing organic matters in strong acid vanadium solution |
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