CN103172108B - Method and system for separating metal sulfide from waste liquid and recovering ammonia water - Google Patents
Method and system for separating metal sulfide from waste liquid and recovering ammonia water Download PDFInfo
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- CN103172108B CN103172108B CN201210070706.6A CN201210070706A CN103172108B CN 103172108 B CN103172108 B CN 103172108B CN 201210070706 A CN201210070706 A CN 201210070706A CN 103172108 B CN103172108 B CN 103172108B
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- waste liquid
- sulfide
- ammoniacal liquor
- heating
- ammonia water
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- 239000007788 liquid Substances 0.000 title claims abstract description 108
- 239000002699 waste material Substances 0.000 title claims abstract description 108
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 14
- 238000000224 chemical solution deposition Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052981 lead sulfide Chemical group 0.000 claims description 2
- 229940056932 lead sulfide Drugs 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- 150000002500 ions Chemical class 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- -1 sulfur ion Chemical class 0.000 abstract description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
A method and system for separating metal sulfide from waste liquid and recovering ammonia water, the method includes making the sulfur-containing component in the waste liquid release the sulfur ion and form the heating step of the metal sulfide with the metal ion crystallization; a filtering step of separating and removing solid particles from the waste liquid; and a recovery step of recovering ammonia water from the filtered waste liquid. The method utilizes a heating mode to crystallize sulfide ions and metal ions in the waste liquid to form metal sulfides, removes solid particles in the waste liquid through filtration, and then recovers the ammonia water, so that heavy metal ions can be effectively separated, and the influence on the effect and stability of ammonia water recovery due to scaling and blockage of ammonia water recovery equipment caused by the heavy metal ions and the particles can be avoided.
Description
Technical field
The present invention has about a kind of separating metal sulfide in waste liquid and reclaims the method and system of ammoniacal liquor, relates to a kind of separating metal sulfide in the chemical bath deposition processing procedure waste liquid of solar cell especially and reclaims the method and system of ammoniacal liquor.
Background technology
Because earth resources is limited, effectively utilizing greenly the energy of environmental protection can become a kind of trend, and therefore, the application of solar energy source has become a wherein important problem.Solar cell is a kind of optoelectronic semiconductor thin slice utilizing the sunlight direct generation of electricity, wherein copper indium gallium selenide (CopperIndium Gallium Diselenide, referred to as CIGS) thin-film solar cells, it is then efficiency of conversion the best in thin-film solar cells, there is cost simultaneously low, the advantages such as long service life, thus become the focus attracted most attention in solar energy electro-technical field.
In the manufacturing processed of copper-indium-galliun-selenium film solar cell, the waste liquid that electroless plating processing procedure discharges contains many heavy metal ion (such as cadmium, zinc), metal solid particle (such as Cadmium Sulfide), high density ammoniacal liquor, sulfonium ion precursor (such as thiocarbamide) containing sulphur composition and correlated response by product, and wherein high density ammoniacal liquor can utilize vapor removal and condensing mode to give concentrate recycling.But, owing to still containing many heavy metal ion and solid particulate in waste liquid, in ammoniacal liquor recovery system, easily form the problem of fouling or generation blocking, and influential system operation, cause ammoniacal liquor organic efficiency not good.Therefore, be separated the heavy metal ion in removal electroless plating processing procedure waste liquid and solid particulate, become the important factor promoting ammoniacal liquor organic efficiency and maintain ammonia water recovery system stability.
At present, for the heavy metal ion in processing procedure waste liquid, the normal mode utilizing interpolation medicament (such as, sulfide), makes heavy metal ion Precipitation, then is separated; Or utilize the mode of ion exchange resin to be separated heavy-metal ion removal in waste liquid.But, utilize the method for adding medicament heavy-metal ion removal to need additionally to make with medicament, and expend the precipitation of considerable time wait precipitation by metallic ion, and the purity of the metallic compound of Precipitation is not high, is unfavorable for reclaiming or recycling.On the other hand, utilize ion exchange resin by the mode of heavy-metal ion removal in waste liquid, although can the treatment time be shortened, need to increase space requirement, and the suitable complexity of equipment not easy care.
Therefore, easily and fast a kind of and separating metal sulfide reclaim the method for ammoniacal liquor in waste liquid effectively is still needed.
Summary of the invention
In view of this, the object of the present invention is to provide easily and fast a kind of and separating metal sulfide reclaim the method for ammoniacal liquor in waste liquid effectively.
Should in waste liquid separating metal sulfide reclaim the method for ammoniacal liquor, comprise this waste liquid of heating, make the sulfur-bearing composition in this waste liquid discharge sulfonium ion, to form metallic sulfide with metal ion crystallization; Filter this waste liquid through heating, to be separated the solid particulate removed in this waste liquid; And ammoniacal liquor is reclaimed in this waste liquid after filtering.Method of the present invention utilizes the mode of heating, the sulfonium ion in waste liquid and metal ion crystallization is first made to form metallic sulfide, after removing the solid particulate in waste liquid after filtration, carry out ammoniacal liquor recovery again, effectively directly can utilize the sulfur-bearing component separating heavy metal ion in waste liquid, heavy metal ion in waste water and particle can be reduced simultaneously and cause the fouling of ammoniacal liquor recovery system, blocking and affect the effect and stability that ammoniacal liquor reclaims.
The present invention provides again a kind of separating metal sulfide in waste liquid and reclaims the system of ammoniacal liquor, comprising: heating unit, in order to add thermal effluent, makes the sulfur-bearing composition in waste liquid discharge sulfonium ion, and forms metallic sulfide with metal ion crystallization; Filtration unit, in order to the waste liquid after filtering and heating, to be separated the solid particulate removed in this waste liquid; And ammonia water recovery device, in order to reclaim ammoniacal liquor in the waste liquid after inherent filtration.System of the present invention first utilizes heating unit to improve the temperature of waste liquid, makes the sulfur-bearing composition in waste liquid discharge sulfonium ion and form metallic sulfide with metal ion crystallization, and recycling filtration unit removes solid particulate in waste liquid.Because waste liquid first improves the temperature of waste liquid through heating unit, when more contributing to finally utilizing retrieving arrangement to carry out ammoniacal liquor recovery, when particularly utilizing the mode of ammonia removal technology (ammonia stripping) to reclaim ammoniacal liquor, significantly can reduce the energy demand of reclaiming ammoniacal liquor, wherein, what use removes gas for air or steam.On the other hand, because the heavy metal ion in waste liquid first forms metallic sulfide with sulfonium ion crystallization, and it is removable, filtration unit is then separated the solid particulate in this waste liquid, therefore can reduce heavy metal ion in waste liquid and particle and cause the fouling of ammoniacal liquor recovery system, blocking and affect the situation of effect that ammoniacal liquor reclaims and stability.
Embodiment
Describe embodiments of the present invention in detail below by way of particular embodiment, the content that the personage haveing the knack of this skill discloses by specification sheets of the present invention understands advantage of the present invention and effect easily, but not category of the present invention is confined to this.
In a specific examples, the present invention separating metal sulfide the method reclaiming ammoniacal liquor in waste liquid use the chemical bath deposition waste liquid (hereinafter referred to as CBD waste liquid) of CIGS solar cell, carrying out heating, filter and the step such as recovery, recycling by reclaiming ammoniacal liquor in waste liquid.First, this CBD waste liquid first heats through heating unit, makes sulfur-bearing composition in waste liquid, such as thiocarbamide (SC (NH
2)
2), thioacetamide (CH
3sCNH
2) or sodium sulphite (Na
2s), discharge sulfonium ion, to increase the sulfite ion concentration in waste liquid.On the other hand, when heating this CBD waste liquid, because the sulfur-bearing composition in this waste liquid discharges sulfonium ion, add the sulfonium ion concentration in waste liquid, the sulfonium ion in waste liquid and metal ion crystallization can be impelled, form metallic sulfide.As shown in table 1, in waste liquid, each constituent concentration is [Cd
2+]=207ppm, [TU]=575ppm, [NH
4oH]=1M time, Heating temperature is 75 DEG C, and increase when heated, sulfonium ion burst size will improve, and Cadmium Sulfide solid is formed, the removal of favourable cadmium ion.
Generally speaking, in method of the present invention, this heating steps makes waste liquid temperature rise to the scope of 70 to 90 DEG C, preferably rise to the scope of 75 to 80 DEG C, discharge sulfonium ion in order to the sulfonium ion precursor in waste liquid, and with the heavy metal ion in waste liquid, crystallization formed metallic sulfide.Then, the temperature range of 60 to 90 DEG C, be preferably the temperature range of 70 to 80 DEG C, directly utilize filtration unit, such as inorganic thin film, carry out filtration step, in waste liquid, be separated the solid particulate removed in this waste liquid.Finally, then the waste liquid after filtering is sent into ammonia water recovery device, under the temperature condition of 60 to 90 DEG C, utilize the modes such as distillation to carry out ammoniacal liquor recovery.Aforesaid heating steps can adopt fluid bed or heating zone, steam, microwave, oil bath, electric energy or combustion heating process to heat this waste liquid.
Method of the present invention, by adding the mode of thermal effluent, makes the sulfur-bearing composition in waste liquid discharge sulfonium ion and metal ion crystallization forms metallic sulfide; Then, directly filter, separate solid particles in waste liquid, then carry out ammoniacal liquor recovery.Therefore, method of the present invention can not need additionally to add sulfide reagent, or under the condition of minimizing sulfide reagent addition, effectively be separated in waste liquid and remove metal ion, the particularly heavy metal ion such as cadmium, reduces the sulphur content in waste liquid simultaneously, the impurity such as the heavy metal ion in waste liquid can be avoided to cause the situations such as the fouling of follow-up ammoniacal liquor recovery system or blocking, the life-span of ammoniacal liquor recovery system can be extended, promote efficiency and the stability of ammoniacal liquor recovery.In addition, because waste liquid first improves the temperature of waste liquid through heating unit, when more contributing to finally utilizing retrieving arrangement to carry out ammoniacal liquor recovery, when particularly utilizing the mode of ammonia removal technology or distillation to reclaim ammoniacal liquor, the energy demand of reclaiming ammoniacal liquor can significantly be reduced.
On the other hand, compared to the mode of Precipitation metallic sulfide, method of the present invention utilizes the mode of crystallization, makes the metal ion in this waste liquid and sulfonium ion form metallic sulfide, then is separated the solid particulate in this waste liquid via the mode of filtering.Because the heavy metal sulfide purity of this kind of crystallization is higher, be conducive to the recovery of heavy metal, and do not need to expend and wait as long for metallic sulfide precipitation, contribute to promoting overall process efficiency.
The present invention's separating metal sulfide reclaim the system of ammoniacal liquor in waste liquid, comprises heating unit, in order to add thermal effluent, makes the sulfur-bearing composition in waste liquid discharge sulfonium ion, and form metallic sulfide with metal ion crystallization; Filtration unit, in order to the waste liquid after filtering and heating, to be separated removal solid particulate; And ammoniacal liquor and retrieving arrangement, in order to reclaim ammoniacal liquor in the waste liquid after inherent filtration.In system of the present invention, there is no particular restriction for this heating unit, such as, use the general heating unit with whipping device, fluid bed or heating zone, steam, microwave, oil bath, electric energy or combustion heating process maybe can be adopted to heat this waste liquid.
In a specific examples, the present invention separating metal sulfide the heating unit reclaiming ammoniacal liquor system in waste liquid use tubular structure and have the fluid bed of heating function.Pending CBD waste liquid imports this fluid bed from bottom, through heating to the scope of 70 to 90 DEG C, after preferably rising to the scope of 75 to 80 DEG C, precursor containing sulphur composition in waste liquid, such as thiocarbamide, thioacetamide or sodium sulphite, sulfonium ion can be discharged, and impel the sulfonium ion in waste liquid and metal ion, such as cadmium, zinc, copper, indium, nickel or lead, crystallization becomes metallic sulfide, such as Cadmium Sulfide, zinc sulphide, cupric sulfide, indium sulfide, nickelous sulfide and lead sulfide form at least one compound of group; Waste liquid after heating, then flowed out by this fluid bed top exit.In this specific examples, this fluid bed interior visible needs to fill silica sand monomer, and in order to adsorb the metallic sulfide of crystallization in waste liquid, such as Cadmium Sulfide, contributes to being separated the metallic sulfide removing crystallization in waste liquid.
The present invention's separating metal sulfide reclaim in the system of ammoniacal liquor in waste liquid, this filtration unit is connected with the outlet of this heating unit, or is directly arranged at the unloading position of this heating unit.In this specific examples, use resistant to elevated temperatures inorganic filter film as filtration unit, and this inorganic filter film is set directly at the unloading position of this heating unit, directly to carry out filtration step under the high temperature conditions, be separated in this CBD waste liquid and remove solid particulate.If fluid bed inside is filled with silica sand monomer, and adsorb the metallic sulfide of crystallization in waste liquid, then filtration step is mainly separated other solid particulate removed and be suspended in waste liquid.Certainly, if the metallic sulfide containing a small amount of crystallization in waste liquid, also can pass through filtering separation.Wherein inorganic filter film can be ceramic membrane, and pore diameter range 0.1 μm to 1.4 μm, operation can reach more than 90 DEG C, chemical resistance and acid-basicity, and working pressure can reach more than 10bar.
The present invention's separating metal sulfide reclaim in the system of ammoniacal liquor in waste liquid, this CBD waste liquid is through heating devices heat, the sulfonium ion in waste liquid and metal ion crystallization is made to form metallic sulfide, after being separated removal solid particulate via filtration unit again, directly enter ammonia water recovery device, such as distillation tower or gas stripping column, carry out ammoniacal liquor recovery.In this specific examples, the temperature through the CBD waste liquid of heating, filtration maintains more than 60 DEG C usually, directly can carry out ammoniacal liquor recovery, not need to carry out pre-warmed process again, reclaims the required energy consumed of ammoniacal liquor therefore, it is possible to significantly reduce.Other available ammoniacal liquor recovery method also can comprise pyrogenic process, electroosmose process, ion-exchange membrane electrolysis, polypropylene (PP) tubular fibre embrane method, magnesium ammonium phosphate (MgNH
4pO
46H
2o) precipitator method etc.
Embodiment
Emulation waste liquid sample A, B, C of proportions listed by table 22 liters, react, last 15 minutes under the condition of 75 DEG C.After having reacted, respectively by waste liquid sample A, B, C by the entrance charging bottom fluid bed, silica sand carrier crystal seed is filled in fluid bed inside, and carry out heating crystalline, temperature controls in the scope of 75 to 80 DEG C.The fluid bed length used 80 centimeters, diameter 2 centimeters, cell body capacity is 500 milliliters, and silica sand inserts 150 milliliters, and influent stream speed is per minute 10 milliliters, and return velocity is per minute 200 milliliters, and the residence time (HRT) is 50 minutes.After the ceramic membrane of the waste liquid sample via hole diameter 1.4 μm of fluid bed top discharge carries out micro-filtration, analysis ingredient content, calculates the clearance of metal ion, and by outcome record in table 1.The CBD waste liquid of heterogeneity ratio, heating and membrane filtration process is utilized to operate, when former waste liquid cadmium ion and thiocarbamide molecular constituents ratio are more than 1: 8, in waste liquid, cadmium ion clearance can be greater than 95%, after process, in waste liquid, concentration of cadmium ions will be less than 5ppm, effectively can avoid rear end ammonia water recovery system scale effect.Fluid bed system, via after row's crystalline substance, is got Cadmium Sulfide crystal and is utilized X-ray florescence analysis instrument (XRF) to measure purity can to reach more than 90%.
Percent crystallization in massecuite (%):
Clearance (%):
Table 2
The cadmium ion of the present embodiment is from Cadmium Sulphate (also can be prepared by cadmium acetate, Cadmium chloride fine powder, cadmium nitrate or cyanogen ammonification cadmium).
S.S. (suspended solid): suspended solids
Dis [Cd
2+]: solubilised state concentration of cadmium ions
T [Cd
2+]: total concentration of cadmium ions
Embodiment result shows, at not outer adding medicine and preheating CBD waste liquid under 75-80 DEG C of condition, namely can crystallization, filtration supervisor, SS contained by waste liquid and cadmium ion are effectively removed.So, SS, cadmium ion can be avoided to block with incrustation in the pipeline, column internals of ammoniacal liquor recovery system, significantly reduce the frequency of recovery system maintenance, with the stability reclaiming ammoniacal liquor operation of equipment.
Claims (13)
1. separating metal sulfide reclaim the method for ammoniacal liquor in the chemical bath deposition waste liquid of CIGS solar cell, comprises the following steps:
Heat this waste liquid, make the sulfur-bearing composition in this waste liquid discharge sulfonium ion, to form metallic sulfide with metal ion crystallization, wherein, this sulfur-bearing composition is thiocarbamide;
Filter this waste liquid through heating, to be separated the solid particulate removed in this waste liquid; And
Ammoniacal liquor is reclaimed in this waste liquid after filtering.
2. method according to claim 1, is characterized in that, this Heating temperature is between the scope of 70 to 90 DEG C.
3. method according to claim 1, is characterized in that, this metal ion comprises cadmium, zinc, copper, indium, nickel or lead metal ion.
4. method according to claim 1, is characterized in that, the crystal metal sulfide formed be selected from Cadmium Sulfide, zinc sulphide, cupric sulfide, indium sulfide, nickelous sulfide and lead sulfide form at least one compound of group.
5. method according to claim 1, is characterized in that, this filters and carries out under the temperature condition of 60 to 90 DEG C.
6. method according to claim 1, is characterized in that, uses inorganic thin film to filter.
7. method according to claim 1, is characterized in that, this carries out under being recovered in the temperature condition of 60 to 90 DEG C.
8. method according to claim 1, is characterized in that, utilizes the mode of distillation or ammonia removal technology to reclaim ammoniacal liquor.
9. separating metal sulfide reclaim the system of ammoniacal liquor in the chemical bath deposition waste liquid of CIGS solar cell, comprising:
Heating unit, in order to heat this waste liquid;
Filtration unit, is arranged at the unloading position of this heating unit, and this filtration unit in order to filter this through heating after waste liquid; And
The retrieving arrangement of ammoniacal liquor, in order to reclaim ammoniacal liquor in this waste liquid after filtering.
10. system according to claim 9, is characterized in that, this heating unit is fluid bed.
11. systems according to claim 10, is characterized in that, this fluid bed inside is filled with silica sand.
12. systems according to claim 9, is characterized in that, this filtration unit is inorganic filter film.
13. systems according to claim 9, is characterized in that, this ammonia water recovery device is distillation tower or gas stripping column.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100147321 | 2011-12-20 | ||
| TW100147321A TWI409223B (en) | 2011-12-20 | 2011-12-20 | System and method for separating metal sulfide and recycling ammonium hydroxide from waste water |
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| CN103172108A CN103172108A (en) | 2013-06-26 |
| CN103172108B true CN103172108B (en) | 2015-11-04 |
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| TW (1) | TWI409223B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106637294B (en) * | 2016-12-30 | 2018-09-11 | 四川师范大学 | The method for decoppering of nickel solution |
| CN107043853A (en) * | 2016-12-30 | 2017-08-15 | 四川师范大学 | The dezincification method of copper solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091076C (en) * | 1999-04-08 | 2002-09-18 | 柳州市环境保护科学研究所 | Process for treating sewage containing Zn and Cd |
| TW200621651A (en) * | 2004-12-30 | 2006-07-01 | Aquatech Corp | Apparatus and method of treating heavy-metal-containing wastewater with sulfidizing agent |
| CN101391799A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for recovery processing of ammonia nitrogen from printed circuit board waste liquid |
| CN101984097A (en) * | 2010-11-24 | 2011-03-09 | 苏州市环境工程有限责任公司 | Method for comprehensive recovery of heavy metal from spent solder stripper |
| CN102145964A (en) * | 2011-03-31 | 2011-08-10 | 北京大学 | Method for treating high-ammonia-nitrogen beryllium-containing waste water |
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2011
- 2011-12-20 TW TW100147321A patent/TWI409223B/en active
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2012
- 2012-03-16 CN CN201210070706.6A patent/CN103172108B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091076C (en) * | 1999-04-08 | 2002-09-18 | 柳州市环境保护科学研究所 | Process for treating sewage containing Zn and Cd |
| TW200621651A (en) * | 2004-12-30 | 2006-07-01 | Aquatech Corp | Apparatus and method of treating heavy-metal-containing wastewater with sulfidizing agent |
| CN101391799A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for recovery processing of ammonia nitrogen from printed circuit board waste liquid |
| CN101984097A (en) * | 2010-11-24 | 2011-03-09 | 苏州市环境工程有限责任公司 | Method for comprehensive recovery of heavy metal from spent solder stripper |
| CN102145964A (en) * | 2011-03-31 | 2011-08-10 | 北京大学 | Method for treating high-ammonia-nitrogen beryllium-containing waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201326050A (en) | 2013-07-01 |
| CN103172108A (en) | 2013-06-26 |
| TWI409223B (en) | 2013-09-21 |
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