CN102351294A - Method for treating arsenic in waste water - Google Patents
Method for treating arsenic in waste water Download PDFInfo
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- CN102351294A CN102351294A CN2011101975946A CN201110197594A CN102351294A CN 102351294 A CN102351294 A CN 102351294A CN 2011101975946 A CN2011101975946 A CN 2011101975946A CN 201110197594 A CN201110197594 A CN 201110197594A CN 102351294 A CN102351294 A CN 102351294A
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- arsenic
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- iron
- waste water
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 178
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 137
- 150000002500 ions Chemical class 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002910 solid waste Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- 230000001143 conditioned effect Effects 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 36
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- 238000000975 co-precipitation Methods 0.000 abstract description 44
- -1 iron ions Chemical class 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 3
- 239000000243 solution Substances 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 22
- 238000010907 mechanical stirring Methods 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 238000002386 leaching Methods 0.000 description 12
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 229940037003 alum Drugs 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 7
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001448 ferrous ion Inorganic materials 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- FGIWMSAVEQNPPQ-UHFFFAOYSA-N arsenic;hydrate Chemical compound O.[As] FGIWMSAVEQNPPQ-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- 229910052964 arsenopyrite Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000012976 tarts Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical group O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KKPLQJMNSIUAFP-UHFFFAOYSA-N ac1mtmt6 Chemical compound S=[As][As]=S KKPLQJMNSIUAFP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- JTEISIQYUPOOLG-UHFFFAOYSA-N arsenic;sulfane Chemical compound S.S.S.[As].[As] JTEISIQYUPOOLG-UHFFFAOYSA-N 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000005538 encapsulation Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 150000001457 metallic cations Chemical class 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010863 uranium mill tailing Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the technical field of wet-process metallurgy and environment protection and particularly relates to a method for treating arsenic in waste water. Solution containing iron ions is added into arsenious solution so that the molar ratio of Fe ions to As ions is 1 to 5 at 15 to 75 DEG C, the mixed solution is uniformly stirred, the pH value of a reaction system is regulated to be 2 to 12 by alkali, in addition, the reaction system continuously takes reaction for 0.17 to 72h at the pH value, and arsenious sediments in the first step are formed; metal ion solution is continuously added in the arsenious sediments formed in the first step so that the molar ratio of metal ions to As ions is 0.1 to 5 at 15 to 75 DEG C, then, the pH value of the reaction system is regulated to be 2 to 12 by alkali, the final arsenious sediments are formed, and As ions in the waste water form high-stability arsenious solid wastes. The two-step coprecipitation method is used, the arsenic removal effect of the waste water is ensured, simultaneously, the stability of the arsenious solid wastes is improved, and the risk of the secondary pollution of arsenious waste residues is greatly reduced.
Description
Technical field
The invention belongs to hydrometallurgy and environmental technology field, a kind of specifically method of handling arsenic in the waste water.
Background technology
Arsenic is a kind of poisonous element, and it often appears in base metal ore and the concentrate.The average abundance of arsenic in the earth's crust is 5mg/L, and the kind of occurring in nature arsenic-containing ores is kind more than 400 (Riveros, P.A. nearly; Dutrizac, J.E.; Spencer; P.Arsenic disposal practices in the metallurgical industry.Can.Metall.Q.2001; 40; 395-420.); And mostly arsenic be to exist with the form of associated mineral with other metals (like Zn, Cu, Ni etc.), nonmetal (S etc.), mainly comprises arsenopyrite (FeAsS), realgar (AsS), orpiment (As
2S
3) etc.In nonferrous metallurgical process, arsenic gets into flue dust with the white arsenic form and is captured in roasting process, perhaps in wet smelting process, is dissolved and enters into the metal raffinate.Therefore, in nonferrous metallurgical process, will form the acidic arsenic-containing waste water of a large amount of high densitys, the arsenic of this moment mainly is that the form with arsenate exists (Langmuir, D.; Mahoney, J.; MacDonald, A.; Rowson J.Predicting arsenic concentrations in the porewaters of buried uranium mill tailings.Geochim.Cosmochim.Acta 1999,63,3379-3394.).Directly be not discharged in the environment if these acid waste waters are treated, not only pollute the environment, but also human and vegeto-animal existence and health in serious threat.The underground water that the long-term drinking arsenic concentration exceeds standard can cause arseniasis, causes the generation of diseases such as skin carcinoma, cardiovascular disorder, diabetes and nervous system disorders.Therefore the removal of arsenic and technique for fixing all are one of research focus for a long time in the Non-ferrous Metallurgy research field, and the safe handling technology that contains the arsenic waste has caused the great attention of states such as comprising China, Japan, the U.S., Canada.
The method of removing arsenic in the polluted-water has a lot, for example: the precipitator method, absorption method, ion-exchange/reverse osmosis method, cementation method, biochemical process etc.Handle at present industry metallurgy waste water institute generally the method for employing be the co-precipitation of iron arsenic; It has the clearance height (in Fe/As＞3 o'clock; [As]＜0.5mg/L; Can reach the existing trade effluent arsenic emission standard of China), characteristics such as easy and simple to handle, economical and practical, Environmental Protection Agency (EPA) is called this method " the best is proved techniques available " (The Best Demonstrated Availed Technology).The waste water arsenic removal process that worldwide is widely used in nonferrous metallurgy and sulfuric acid industry.At present; Mainly concentrate on aspects such as arsenic removal technology, the formed stability that contains the arsenic coprecipitate and solubleness for the research of the solid arsenic of iron arsenic coprecipitation method arsenic removal; Early stage result of study shows; The high more formed stability that contains the arsenic coprecipitate of Fe/As mol ratio is strong more; Along with the prolongation of time, the content that is discharged into the arsenic in the liquid phase again is low more; Use the optimal ph scope of this kind method arsenic removal to be slightly acidic zone (pH 3～5), however in industrial arsenic removal process, the pH value need be controlled at weakly alkaline zone (pH 7～9) usually so that other metallic cations that contained in the waste water (like Cu
2+, Ni
2+, Co
2+, Pb
2+Deng) can form precipitation of hydroxide separately and removed simultaneously.But a large amount of chemical form that contains arsenic in the arsenic industrial residue that in iron arsenic coprecipitation process, produces it be unclear that; Its stability is also relatively poor; Cause serious secondary arsenic contamination easily; To have a volume of storing up excessive as containing the arsenic carrier with this, solid arsenic amount low (＜6%) of carrier and shortcoming such as less stable under reductive condition.And when arsenic content in the waste water is very high when simultaneously iron level is low, with arsenic with crystal form scorodite (FeAsO
42H
2O) form is removed the method that is now to be taked usually.Have arsenic content height in the solid with this as solid arsenic carrier, need advantages such as the iron amount is few, dehydration property is better.But investigators exist bigger dispute for the stability of scorodite; The solubleness of having reported about scorodite; Maximum gap has reached four one magnitude; This mainly is (scorodite of amorphous, crystallization degree difference or highly crystalline) (Bluteau, the M.C. that character caused by formed scorodite self; Demopoulos, G.P.The incongruent dissolution of scorodite-solubility, kinetics and mechanism.Hydrometallurgy 2007,87,163-177.).Existing result of study shows: the dissolving of congruence property only takes place in scorodite when pH=2; And in the non-congruence property dissolving of the next generation of other conditions; Thereby the release phenomenon of arsenic takes place; For example: the solubleness of scorodite is respectively 1.0 and 5.8mg/L under pH 6 and 7 conditions; Its solubleness under alkaline condition is then higher; Therefore there is the investigator to think scorodite only just stable (Lagno, F. under the envrionment conditions of pH＜7; Rocha, S.D.F.; Chryssoulis, S.; Demopoulos, G.P.Scorodite encapsulation by controlled deposition of aluminum phosphate coatings.J.Hazard.Mater.2010,181,526-534.).
The up-to-date progress that contains the method for arsenic solid waste stability about raising mainly concentrates on following two aspects: first kind is " active ", and this kind method is to realize containing the stable this purpose that increases of arsenic coprecipitate through changing the technological process that forms the co-precipitation of iron arsenic.Found that the iron - arsenic coprecipitate was made basic by the acid, if in the middle of a value (such as pH 4) stabilization period of time (such as 1 day, 1 week), the pH value and then coprecipitated adjusted to 8, in that way that the coprecipitate formed arsenic will improve the stability, the method is also called two-stage method and precipitation; By contrast, conventional pH without intermediate The method is called the value of staying single-stage and precipitation (Jia, YF; Demopoulos, GPCoprecipitation of arsenate with iron (III) in aqueous sulfate media: effect of time, lime as base and co-ions on arsenic retention.Water Res.2008 ,42,661-668.); second is "passive", the method is first formed under the high temperature conditions arsenic coprecipitate - scorodite, then wrapped in aluminum phosphate pre-formed surface scorodite, experimental results showed that: either the oxidizing conditions or under reducing conditions in the formed aluminum phosphate wrapped scorodite stone have high stability, but this kind of method has the problem off aluminum phosphate, Leetmaa (2008) instead of aluminum phosphate, colloidal aluminum wrapping for the same procedure, but in the method of the formed precipitate arsenic in the reducing environment of stability and whether it will produce colloidal aluminum shedding issues remain to be further studied.In fact; The permanent stability of arsenic-containing waste residue are subjected to the influence of many factors; For example: the character of arsenic-containing waste residue self (the pH value the when content of iron, arsenic, calcium and other elements, deposition etc.), the oxide compound that exists in the environment, sulfide, muriate and organic complexing agent etc.Along with various countries bring up to 10 μ g/L with tap water arsenic standard from 50 μ g/L, seek and a kind ofly have higher stability simultaneously and than the trend that the arsenic carrier is the solid arsenic technical development of following metallurgical waste water arsenic removal that contains of low solubility.
Summary of the invention
The object of the invention is to provide a kind of method of handling arsenic in the waste water.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of method of handling arsenic in the waste water: in arsenic containing solution, add the iron content ion solution; Under 15-75 ℃; Making Fe ion and As ionic mol ratio is 1-5; After stirring; Use the pH value of alkali conditioned reaction system to be 2-12; And make reaction system under this pH value, continue reaction 0.17-72 hour, what form the first step contains the arsenic coprecipitate;
Containing of having formed continue to add metal ion solution in the arsenic coprecipitate to the first step; Under 15-75 ℃; Making metal ion and As ionic mol ratio is 0.1-5; Then use the pH value of alkali conditioned reaction system to be 2-12; Form the final arsenic coprecipitate that contains, what make that As ion in the waste water forms high stability contains the arsenic solid waste.
Said iron content ion solution is ferric sulfate, iron nitrate, iron(ic) chloride, ferrous sulfate, Iron nitrate or the iron protochloride that has any crystal water.Said iron content ion solution is preferably ferric sulfate, iron nitrate or iron(ic) chloride.
Described metal ion solution is divalence or trivalent metal ion solution.Described metal ion solution is Tai-Ace S 150, aluminum nitrate, aluminum chloride, ferric sulfate, iron nitrate, iron(ic) chloride, ferrous sulfate, Iron nitrate, iron protochloride, gallium sulfate, gallium nitrate, gallium chloride or the rare earth metal that has any crystal water.
Described rare earth metal can be lanthanum sulfat, lanthanum nitrate, Lanthanum trichloride, cerous sulfate, cerous nitrate or Cerium II Chloride.Described metal ion solution is preferably: Tai-Ace S 150, aluminum nitrate, aluminum chloride, ferric sulfate, iron nitrate or iron(ic) chloride.
The pH value scope that contains the arsenic coprecipitate of said formation is 2-12.The alkali of said conditioned reaction system pH is sodium hydroxide, calcium oxide suspension liquid or Natural manganese dioxide suspension liquid.
The effect that the present invention had: the present invention is through forming the iron arsenic co-precipitation of the first step in lower Fe/As mol ratio and under certain pH value condition; The method that in system, adds the additional metals solion subsequently and make it to take place the second step co-precipitation forms the final arsenic coprecipitate that contains; Main with solving with the formed stability problem that contains the arsenic solid waste after the arsenic removal in the waste water, reduce the secondary pollution that it causes environment; Operation is simple in the present invention simultaneously, mild condition.
Description of drawings
Fig. 1 is the embodiment of the invention after containing of providing, the arsenic co-precipitation formed, and along with the prolongation of time, (wherein that the numeral of sample number into spectrum subscript is the Fe that is added, the stoichiometric ratio of Al and As to be discharged into the content synoptic diagram of the arsenic in the liquid phase again.Fe
4As
1Expression be that the solution of tart Fe/As=4 is neutralized to pH 8 through a step deposition; Fe
2As
1Fe
2, Fe
2As
1Al
1.5, Fe
2As
1Al
2What represent is two step coprecipitates, and the solution with tart Fe/As=2 is neutralized to pH 4 earlier, adds Fe or Al subsequently, is neutralized to pH 8 at last).
Fig. 2 for the embodiment of the invention provide at well-oxygenated environment, the various synoptic diagram that contain the arsenic coprecipitate leaching behind balance 72h stability under different pH condition (wherein with NaOH or CaO as neutralization reagent).
Fig. 3 for the embodiment of the invention provide at well-oxygenated environment, the leaching stability synoptic diagram of co-precipitation under pH 5 and pH 8 conditions (wherein the leaching agent is a distilled water, every change the leaching agent once) at a distance from 24h.
Fig. 4 goes on foot the stable comparison diagram of Fe-As coprecipitate under the chemical reduction condition for what the embodiment of the invention provided at two step Fe-As-Al coprecipitates and.(wherein reductive condition is S/As=20, and pH 7, and the content of arsenic is 100mg/L in the co-precipitation, and what red represented is the chemical reduction condition; What ox represented is oxidizing condition).
Embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme.
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use.
With Fe
2(SO
4)
3XH
2O is dissolved in and is configured to the storing solution that concentration of iron is 12.0g/L in the distilled water, and is for use; With Al
2(SO
4) 18H
2O is dissolved in and is configured to the storing solution that aluminum concentration is 9.52g/L in the distilled water, and is for use.
In the above-mentioned arsenical solution that configures, add the pre-configured ferrum sulfuricum oxydatum solutum of 62.2mL; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add the pre-configured alum liquor of 37.8mL; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 4 always; Then with the 1M NaOH solution pH value of conditioned reaction system once more; Make it reach 8; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask; The final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(referring to Fig. 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 1.5; In adding aluminum ions process, keep reaction system pH is 4 always; Then with the 1M NaOH solution pH value of conditioned reaction system once more; Make it reach 8; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask; The final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
1.5(referring to Fig. 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 4 always; Then with the 1M NaOH solution pH value of conditioned reaction system once more; Make it reach 8; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask; The final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Fe
2(referring to Fig. 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; Adding 5% white lime solution (joins the calcium hydroxide solid in the distilled water; Stirring after 0.5-6 hour and to form) the pH value of conditioned reaction system is 4, that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 4 always; Then with the 5% white lime solution pH value of conditioned reaction system once more; Make it reach 8; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask; The final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(CaO) (referring to Fig. 2).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 5, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 5 always; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(pH 5) (referring to table 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 6, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 6 always; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(pH 6) (referring to table 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 7, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 7 always; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(pH7) (referring to table 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 8, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In adding aluminum ions process, keep reaction system pH is 8 always; Continue to stir and make the As ion form the coprecipitate of high stability after 1 hour; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
2As
1Al
2(pH 8) (referring to table 1).
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add copperas solution; Under 25 ℃; Making inferior Fe ion and As ionic mol ratio is 2; In the process that adds ferrous ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
In the above-mentioned arsenical solution that configures, add pre-configured ferric chloride Solution; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add solution of ferrous chloride; Under 25 ℃; Making inferior Fe ion and As ionic mol ratio is 2; In the process that adds ferrous ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Embodiment 11
In the above-mentioned arsenical solution that configures, add pre-configured iron nitrate solution; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add aluminum nitrate solution; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In the process that adds ferrous ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Embodiment 12
In the above-mentioned arsenical solution that configures, add pre-configured copperas solution; Under 25 ℃; Making inferior Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add alum liquor; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In the process that adds ferrous ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Embodiment 13
In the above-mentioned arsenical solution that configures, add pre-configured solution of ferrous chloride; Under 25 ℃; Making inferior Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add liquor alumini chloridi; Under 25 ℃; Making Al ion and As ionic mol ratio is 2; In the process that adds ferrous ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Embodiment 14
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add gallium sulfate solution; Under 25 ℃; Making gallium ion and As ionic mol ratio is 2; In the process that adds gallium ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Embodiment 15
In the above-mentioned arsenical solution that configures, add pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃, making Fe ion and As ionic mol ratio is 2, under the mechanical stirring condition; The pH value that adds 1M NaOH solution conditioned reaction system is 4, and that stirs 1 hour formation the first step contains the arsenic coprecipitate;
In forming the system that contains the arsenic coprecipitate, continue to add lanthanum sulfat solution; Under 25 ℃; Making lanthanum ion and As ionic mol ratio is 2; In the process that adds lanthanum ion, keep reaction system pH is 4 always; Then, make it reach 8, continue to stir the coprecipitate that makes As ion formation high stability after 1 hour with the pH value of 1M NaOH solution conditioned reaction system; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL.
Comparative example 1
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use.
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 4; Under the mechanical stirring condition; Using the pH value of 1M NaOH solution conditioned reaction system is 8, continues to stir to form after 1 hour to contain the arsenic coprecipitate, subsequently it is transferred in the triangular flask; The final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
4As
1
Comparative example 2
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use;
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 4; Under the mechanical stirring condition, be 8 with the pH value of 5% white lime solution (the calcium hydroxide solid is joined in the distilled water, stir after 0.5-6 hour form) conditioned reaction system; Continue to stir to form after 1 hour and contain the arsenic coprecipitate; Subsequently it is transferred in the triangular flask, the final volume of co-precipitation is 500mL, makes Fe with the formed arsenic coprecipitate note that contains of this kind method
4As
1(CaO).
Comparative example 3.
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use;
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; Using the pH value of 1M NaOH solution conditioned reaction system is 5; Continuation is stirred to form after 1 hour and is contained the arsenic coprecipitate, makes Fe with the formed aluminum ion arsenic coprecipitate note that contains before that do not add of this kind method
2As
1(pH 5).
Comparative example 4
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use;
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; Using the pH value of 1M NaOH solution conditioned reaction system is 6; Continuation is stirred to form after 1 hour and is contained the arsenic coprecipitate, makes Fe with the formed aluminum ion arsenic coprecipitate note that contains before that do not add of this kind method
2As
1(pH 6).
Comparative example 5
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use;
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; Using the pH value of 1M NaOH solution conditioned reaction system is 7; Continuation is stirred to form after 1 hour and is contained the arsenic coprecipitate, makes Fe with the formed aluminum ion arsenic coprecipitate note that contains before that do not add of this kind method
2As
1(pH 7).
Comparative example 6
With Na
3AsO
412H
2O is dissolved in and is configured to the storing solution that arsenic concentration is 7.34g/L in the distilled water, and that gets 68.1mL contains arsenic storing solution (initial arsonium ion concentration be 1g/L) to the large beaker of 500mL, subsequently to wherein adding 2.5mL 6M H
2SO
4Solution, making the pH value of arsenic containing solution is～1.5, for use;
Then to wherein adding pre-configured ferrum sulfuricum oxydatum solutum; Under 25 ℃; Making Fe ion and As ionic mol ratio is 2; Under the mechanical stirring condition; Using the pH value of 1M NaOH solution conditioned reaction system is 8; Continuation is stirred to form after 1 hour and is contained the arsenic coprecipitate, makes Fe with the formed aluminum ion arsenic coprecipitate note that contains before that do not add of this kind method
2As
1(pH 8).
Table 1 is the experimental result of embodiment 5-8 and comparative example 3-6
Can know Fe by Fig. 1
2As
1Al
2Be embodiment 1, Fe
2As
1Al
1.5Be embodiment 2, Fe
2As
1Fe
2Be embodiment 3, Fe
4As
1Be comparative example 1.The method of traditional removal arsenic-containing waste water forms the co-precipitation of iron arsenic, just Fe with Fe/As>=4 usually
4As
1Guarantee the clearance of arsenic and the stability that contains the arsenic coprecipitate with this, but the permanent stability of this kind co-precipitation are not very good, as can be seen from Figure 1; After this co-precipitation was stored up 60 days, the arsenic content that is discharged into again in the liquid phase had just reached～32mg/L.
And two the step co-precipitation are formed contains the release phenomenon again that the arsenic coprecipitate can suppress arsenic significantly.If second step is with iron ion (Fe
2As
1Fe
2) form the final arsenic coprecipitate that contains, it can reduce the burst size again of about 1/3rd arsenic, and if second step with aluminum ion (Fe
2As
1Al
1.5) forming the final arsenic coprecipitate that contains, the content that is discharged into the arsenic in the liquid phase after 120 days again is 11.0mg/L, and if continue to strengthen the consumption (Fe of aluminium
2As
1Al
2), the content that was discharged into the arsenic in the liquid phase in 120 days afterwards again only is 3.2mg/L.
Can know Fe by Fig. 2
2As
1Al
2Be embodiment 1, Fe
2As
1Al
2(CaO) be embodiment 4, Fe
4As
1Be comparative example 1, Fe
4As
1(CaO) be comparative example 2.As can be seen from Figure 2, using the resulting arsenic coprecipitate that contains of two step coprecipitation methods to have higher leaching stability, is under the 6-9 condition in the pH value, and its solubleness is than the low one magnitude of a step co-precipitation.All arsenic coprecipitates that contain all have higher leaching stability under acidic conditions.Formed co-precipitation all has advantages of higher stability as alkali with CaO, and no matter it is by a step or formed by two step coprecipitation process.
Can know Fe by Fig. 3
2As
1Al
2Be embodiment 1, Fe
2As
1Al
2(CaO) be embodiment 4, Fe
4As
1Be comparative example 1, Fe
4As
1(CaO) be comparative example 2.Can know by Fig. 3; Leaching pH value is 5 o'clock; The stability of various co-precipitation does not have too significantly difference; After having replaced ten leaching agent; The content of the arsenic that various co-precipitation discharge in liquid phase is all less than 0.1mg/L; And when leaching pH value is 8, have lower leaching solubleness with the formed arsenic coprecipitate that contains of two step coprecipitation methods, confirmed that further it has higher stability under oxidizing condition.As can be seen from the figure for Fe
4As
1(NaOH) co-precipitation, its content that is discharged into the arsenic in the liquid phase has been up to 151.8mg/L, and through ten times repeatedly behind the leaching, its numerical stability is about 10mg/L, and for Fe
2As
1Al
2(NaOH) co-precipitation, contains in the arsenic coprecipitate at four kinds and to have the highest stability about 0.1mg/L through its numerical value all-the-time stable behind ten leachings.
Can know Fe by Fig. 4
2As
1Al
2Be embodiment 1, Fe
4As
1Be comparative example 1.As can be seen from Figure 4, the formed arsenic coprecipitate (Fe that contains of a step co-precipitation
4As
1) less stable under the chemical reduction condition; After 7 days; The content that is discharged into the arsenic in the liquid phase has just reached～80mg/L; Be equivalent to discharge 80% the total arsenic in the arsenic co-precipitation solid of containing; The arsenic major part that is discharged all is a pentavalent arsenic; Be trivalent arsenic only less than 5% arsenic; And contain the arsenic co-precipitation and have a relative advantages of higher stability in that reductive condition is next through two step co-precipitation are formed; The content of the arsenic that discharges after 7 days be～22mg/L, this numerical value only be precipitate in a step discharged 1/4th.And the reason that causes arsenic to discharge again is that trivalent Fe is reduced into divalence Fe in the solid.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. method of handling arsenic in the waste water; It is characterized in that: in arsenic containing solution, add the iron content ion solution; Under 15-75 ℃; Making Fe ion and As ionic mol ratio is 1-5; After stirring; Use the pH value of alkali conditioned reaction system to be 2-12, and make reaction system under this pH value, continue reaction 0.17-72 hour, what form the first step contains the arsenic coprecipitate;
Containing of having formed continue to add metal ion solution in the arsenic coprecipitate to the first step; Under 15-75 ℃; Making metal ion and As ionic mol ratio is 0.1-5; Then use the pH value of alkali conditioned reaction system to be 2-12; Form the final arsenic coprecipitate that contains, what make that As ion in the waste water forms high stability contains the arsenic solid waste.
2. by the method for arsenic in the described processing waste water of claim 1, it is characterized in that: said iron content ion solution is ferric sulfate, iron nitrate, iron(ic) chloride, ferrous sulfate, Iron nitrate or the iron protochloride that has any crystal water.
3. by the method for arsenic in the described processing waste water of claim 2, it is characterized in that: said iron content ion solution is preferably ferric sulfate, iron nitrate or iron(ic) chloride.
4. by the method for arsenic in the described processing waste water of claim 1, it is characterized in that: described metal ion solution is divalence or trivalent metal ion solution.
5. by the method for arsenic in the described processing waste water of claim 4, it is characterized in that: described metal ion solution is Tai-Ace S 150, aluminum nitrate, aluminum chloride, ferric sulfate, iron nitrate, iron(ic) chloride, ferrous sulfate, Iron nitrate, iron protochloride, gallium sulfate, gallium nitrate, gallium chloride or the rare earth metal that has any crystal water.
6. by the method for arsenic in the described processing waste water of claim 5, it is characterized in that: described rare earth metal can be lanthanum sulfat, lanthanum nitrate, Lanthanum trichloride, cerous sulfate, cerous nitrate or Cerium II Chloride.
7. by the method for arsenic in the described processing waste water of claim 4, it is characterized in that: described metal ion solution is preferably: Tai-Ace S 150, aluminum nitrate, aluminum chloride, ferric sulfate, iron nitrate or iron(ic) chloride.
8. by the method for arsenic in the described processing waste water of claim 1, it is characterized in that: the pH value scope that contains the arsenic coprecipitate of said formation is 2-12.
9. by the method for arsenic in the described processing waste water of claim 1, it is characterized in that: the alkali of said conditioned reaction system pH is sodium hydroxide, calcium oxide suspension liquid or Natural manganese dioxide suspension liquid.
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| CN108138258A (en) * | 2015-09-02 | 2018-06-08 | 摩利博德诺斯伊金属股份公司 | The method of arsenic removal from arsenic material |
| CN110606512A (en) * | 2019-10-21 | 2019-12-24 | 中国科学院沈阳应用生态研究所 | Method for stabilizing arsenic-calcium slag |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102296A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院长春应用化学研究所 | The purifying method of waste water containing arsenic |
| CN1155519A (en) * | 1996-01-16 | 1997-07-30 | 三菱重工业株式会社 | Process for treating arsenic-containing waste water |
| CN1473771A (en) * | 2003-08-06 | 2004-02-11 | 中国地质大学（武汉） | Method for removing arsenic and cadmium from waste water |
| CN1733616A (en) * | 2004-08-11 | 2006-02-15 | 北京精密单因子水工程技术有限公司 | Arsenic comprising groundwater processing method |
-
2011
- 2011-07-14 CN CN201110197594.6A patent/CN102351294B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102296A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院长春应用化学研究所 | The purifying method of waste water containing arsenic |
| CN1155519A (en) * | 1996-01-16 | 1997-07-30 | 三菱重工业株式会社 | Process for treating arsenic-containing waste water |
| CN1473771A (en) * | 2003-08-06 | 2004-02-11 | 中国地质大学（武汉） | Method for removing arsenic and cadmium from waste water |
| CN1733616A (en) * | 2004-08-11 | 2006-02-15 | 北京精密单因子水工程技术有限公司 | Arsenic comprising groundwater processing method |
Non-Patent Citations (2)
| Title |
|---|
| 《WATER RESEARCH》 20070825 Yongfeng Jia et al. "Coprecipitation of arsenate with iron(Ⅲ) in aqueous sulfate media: Effect of time, lime as base and co-ions on arsenic retention" 661-668 1-4 , 第42期 * |
| YONGFENG JIA ET AL.: ""Coprecipitation of arsenate with iron(Ⅲ) in aqueous sulfate media: Effect of time, lime as base and co-ions on arsenic retention"", 《WATER RESEARCH》 * |
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| CN110643815A (en) * | 2019-09-05 | 2020-01-03 | 紫金矿业集团股份有限公司 | Recycling harmless treatment method for black copper mud |
| CN110606512A (en) * | 2019-10-21 | 2019-12-24 | 中国科学院沈阳应用生态研究所 | Method for stabilizing arsenic-calcium slag |
| CN110606512B (en) * | 2019-10-21 | 2022-03-22 | 中国科学院沈阳应用生态研究所 | Method for stabilizing arsenic-calcium slag |
| CN111889488A (en) * | 2020-08-03 | 2020-11-06 | 中国科学院沈阳应用生态研究所 | Method for stabilizing waste residue |
| CN111889488B (en) * | 2020-08-03 | 2021-08-24 | 中国科学院沈阳应用生态研究所 | Method for stabilizing waste residue |
| CN111957731A (en) * | 2020-08-14 | 2020-11-20 | 中国科学院沈阳应用生态研究所 | Sulfur-induced stabilization treatment method for iron-rich arsenic-polluted soil |
| CN113072211A (en) * | 2021-04-01 | 2021-07-06 | 云南黄金矿业集团股份有限公司 | Method for treating high-arsenic ferrate wastewater and recovering copper and iron |
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