CN107417004A - A kind of method of advanced treating acid waste water containing thallium - Google Patents
A kind of method of advanced treating acid waste water containing thallium Download PDFInfo
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- CN107417004A CN107417004A CN201710358414.5A CN201710358414A CN107417004A CN 107417004 A CN107417004 A CN 107417004A CN 201710358414 A CN201710358414 A CN 201710358414A CN 107417004 A CN107417004 A CN 107417004A
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- Prior art keywords
- waste water
- thallium
- advanced treating
- solution
- solid
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- 239000002351 wastewater Substances 0.000 title claims abstract description 99
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 88
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 230000001376 precipitating effect Effects 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000920 calcium hydroxide Substances 0.000 claims description 19
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000002594 sorbent Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 25
- 238000001914 filtration Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 3
- 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 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- -1 has ion-exchange Chemical compound 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 229910021515 thallium hydroxide Inorganic materials 0.000 description 1
- 208000026015 thallium poisoning Diseases 0.000 description 1
- QGYXCSSUHCHXHB-UHFFFAOYSA-M thallium(i) hydroxide Chemical compound [OH-].[Tl+] QGYXCSSUHCHXHB-UHFFFAOYSA-M 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of method of advanced treating acid waste water containing thallium, this method is by after the neutralized precipitation of the waste water, advanced treating is carried out again, pH nertralizers are added to waste water, pH is adjusted to neutrality, adds precipitating reagent, then carry out separation of solid and liquid, supernatant carries out advanced treating after separation of solid and liquid, directly outer can be arranged after being filtered after processing；The present invention can effectively remove the heavy metal thallium in waste water, not only technological process is simple for this method by that alkali neutralization precipitation and advanced treating will be added to be combined, it is easy to operate, non-secondary pollution produces, the μ g/L of and thallium content in processed waste water≤0.1, can be back to production technology or directly outer arrange.
Description
Technical field
The present invention relates to the deep treatment method of field of industrial waste water treatment, more particularly to a kind of acid waste water containing thallium.
Background technology
Thallium（Tl）Belong to association in the metal sulfide such as rare and scatter element, Chang Tie, zinc, copper in the earth's crust, also with organic matter knot
Conjunction form is present in coalfield and oil.The bio-toxicity of high intensity is presented in thallium and its compound, to the toxicity of mammal
It is even stronger than heavy metals such as lead, mercury, easily accumulate in vivo, the exposure of human body excess can cause nervous system, digestive system, skin
The permanent poisoning injury such as skin, hair.
In recent years, due to there occurs a lot of events about thallium poisoning, promoting State Environmental Protection Administration that thallium is included in into ring
Border priority pollutant blacklist, and《Water environment quality standard》（GB 3838-2002）In in water quality thallium standard limit
Value makes clear stipulaties, it is desirable to centralized Drinking Water earth surface water source in water body the concentration of thallium must not be higher than 0.1 μ g/L（Draw
It is 0.5 μ g/L to play poisoning concentration）.
The a large amount of heavy metal containing thallium is produced in the production process of gold hydrometallurgy, lead-zinc smelting and related Mineral Processing Enterprises
Waste water.Found according to Field Research, waste water containing thallium is mainly derived from gold hydrometallurgy production process, gold wet smelting process
All containing various heavies such as thalliums, it is former for caused 4 kinds of typical waste water, such as waste acid, raffinate, lean solution containing cyanogen and smart smelting waste water
Tl contents in water are more than every liter tens to several hectogammas, or even a kilogamma.
The method of processing waste water containing thallium mainly has ion-exchange, extraction, natural evaporation method and chemistry to sink at present at present
Shallow lake method, but be difficult to handle thallium element in waste water to below 0.1 μ g/L, still cause efflux wastewater severe overweight, and earth's surface
Water（Cross section of river）Thallium pollution problem water hygiene is constituted a serious threat safely.
The processing method for the waste water containing thallium that patent CN1067229A is related to, it is that waste water is first adjusted into pH to 2~5, then uses oxygen
Monovalence thallium is oxidized to trivalent thallium by agent, adds coprecipitator, generation thallium hydroxide precipitation, this method can only be by the thallium in waste water
Element is down to 0.05mg/L, it is difficult to meets newest environmental requirement, poor processing effect, processed waste water can not be discharged directly, be needed
Want further advanced treating.
Patent CN104773863A is related to a kind of process for deeper purifying of waste water containing thallium, and waste water containing thallium first adds excess
Monovalence thallium is oxidized to trivalent thallium by oxidant, then wastewater pH is adjusted to 7~13, and separation of solid and liquid obtains supernatant, adds reduction
Adsorption treatment is carried out after agent again, this method can be handled thallium content in waste water to 0.1 μ g/L, high treating effect, but work be present
The shortcomings of skill flow is complicated, reagent cost is high, capital expenditure cost is big, treatment effect is unstable.
The content of the invention
In view of the shortcomings of the prior art, in order to solve the existing processing in the advanced treatment process of acid waste water containing thallium it is not up to standard with
And the problems such as processing technological flow complexity, the present invention propose one kind by adding alkali neutralization precipitation and advanced treating United Technologies to locate
Acid waste water containing thallium is managed, with optimizing process, processing cost, the toxicity of reduction waste water is saved, realizes the depth of heavy metal thallium
Removing, the μ g/L of thallium content in processed waste water≤0.1.
For the above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of method of advanced treating acid waste water containing thallium, using acid waste water containing thallium as process object, utilize neutralization precipitation and depth
Degree processing United Technologies are handled, and finally realize that standard water discharge is discharged.
Comprise the following steps：
（1）PH nertralizers are added into acid waste water containing thallium, wastewater pH is adjusted to neutrality；
（2）To step（1）Precipitating reagent is added after neutralization in waste water, then waste water is passed through solid-liquid separating equipment；
（3）Supernatant after separation of solid and liquid is subjected to advanced treating, further filtered through filter after processing, standard water discharge discharge.
Step（1）The pH nertralizers are carbide slag, milk of lime, magnesium hydroxide solution, sodium hydroxide solution, potassium hydroxide
One or more in solution, sodium carbonate liquor or sodium bicarbonate solution；
Preferably, pH nertralizers are milk of lime；
The concentration 10%~30% of milk of lime；
Preferably, the concentration of milk of lime is 10%~25%.
Step（2）The precipitating reagent is polymeric ferrous sulphate solution, polyaluminium ferrous solution, liquor ferri trichloridi, ferric sulfate
One or more in solution, liquor alumini chloridi or polymeric aluminum chlorides solution, precipitating reagent addition are 0.2%~5%, the reaction time
For 0.5h~6h；
Preferably, precipitating reagent is polymeric ferrous sulphate solution or polyaluminium ferrous solution；
Preferably, the addition of precipitating reagent is 0.5~3%；
Preferably, the reaction time is 1h~6h.
Step（2）The solid-liquid separating equipment is gravitational settler, centrifugal settler, filter press or filter；
Preferably, solid-liquid separating equipment is filter press.
Step（3）The method of the advanced treating is membrane separation process, bioanalysis, electric flocculation method or absorption method；
Preferably, advanced treating is absorption method.
Adsorbent selected by the absorption method is activated carbon, molecular sieve, chitosan, kaolin, polyacrylamide, SK-
One or more in Tl02 type resin sorbents；
Preferably, adsorbent is SK-Tl02 type resin sorbents.
After neutralized precipitation and advanced treating United Technologies processing, the μ g/L of thallium content in waste water≤0.1, life can be back to
Production. art or qualified discharge.
Thallium content is 0.5~10mg/L in the acid waste water containing thallium, and pH is 0.1~2.
Step（1）Middle that pH nertralizers are added into acid waste water containing thallium, wastewater pH, which is adjusted to 7 or so, pH nertralizers, to be
Carbide slag, milk of lime, magnesium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or sodium bicarbonate solution
In one or more, to be cost-effective, preferably milk of lime, the concentration 10%~30% of milk of lime, preferably 10%~25%, example
Such as it is 10%, 15%, 20%, 25%.
Step（2）It is middle that precipitating reagent is added into waste water after neutralization, then waste water is passed through solid-liquid separating equipment；Precipitating reagent can be with
For polymeric ferrous sulphate solution, polyaluminium ferrous solution, liquor ferri trichloridi, ferrum sulfuricum oxydatum solutum, liquor alumini chloridi, aluminium polychloride
One or more in solution, preferably polymeric ferrous sulphate solution or polyaluminium ferrous solution；Precipitating reagent addition be 0.2%~
5%, preferably 0.5~3%, for example, 0.5%, 1%, 2%, 3% etc.；Reaction time is 0.5h~6h, preferably 1h~6h, is, for example,
1h, 2h, 3h, 4h, 5h, 6h etc.；Solid-liquid separating equipment can be gravitational settler, centrifugal settler, filter press or filter, be
Optimization processing technique, preferably filter press.
Step（3）The supernatant that separation of solid and liquid is obtained carries out advanced treating, and processed waste water can be back to production technology
Or direct qualified discharge, the method for advanced treating can be membrane separation process, bioanalysis, electric flocculation method or absorption method, membrane separation process
It is the selective penetrated property using film, according to the difference of the mass transfer selectivity in film of each component in multicomponent fluid, by higher
External pressure, to realize separation, classification, purification or the enrichment to it, micro-filtration, ultrafiltration, nanofiltration and anti-are divided into according to the big I of membrane aperture
Infiltration；Bioanalysis produces a kind of material of flocculent structure similar to activated sludge by cultivating strain on defined medium,
Fully contacted with waste water containing thallium, the flocculating setting with reference to thallium therein, then separate, reach except thallium effect；Electric flocculation method be with
Iron plate or aluminium sheet are anode, and after logical direct current, anode loses electronics, forms metal cation Fe2+、Al3+, gold is generated with OH-
Belong to hydroxide colloid flocculant, the larger flock of generation is combined with heavy metal in waste water, is removed after precipitation or air supporting；Absorption
Method is mainly the powerful suction-operated using adsorbent activity surface area or adsorption group, with metal ion formation ionic bond, altogether
Valence link, chelate etc., then it is filtered remove removing heavy metals reach absorption removing heavy metals purpose；Advanced treating is preferably to adsorb
Method.
The adsorbent that absorption method is selected can be activated carbon, molecular sieve, chitosan, kaolin, polyacrylamide, SK-
One or more in Tl02 type resin sorbents, preferably SK-Tl02 types resin sorbent.
Step（3）The μ g/L of thallium content in filter water outlet≤0.1, non-secondary pollution, production technology or directly can be back to
Qualified discharge.
The preferred scheme of the present invention, comprises the following steps：
（1）Milk of lime is added into acid waste water containing thallium, the concentration of milk of lime is 10%~25%, and wastewater pH is adjusted to 7 or so；
（2）To step（1）Adding polymeric ferrous sulphate solution or polyaluminium ferrous solution in obtained waste water, addition is 0.5%~
3%, 1h~6h is reacted, separation of solid and liquid is carried out through filter press；
（3）Supernatant after separation of solid and liquid is passed through in the adsorption column equipped with SK-Tl02 type resin sorbents, adsorption column water outlet is passed through
Filter filters, and the μ g/L of thallium content≤0.1, can be back to production technology or qualified discharge.
Compared with prior art, the present invention has the effect that：
（1）The invention discloses a kind of new method of advanced treating acid waste water containing thallium, this method passes through neutralization precipitation and depth
Joint processing technology is handled, realizes the deep removal of heavy metal in waste water thallium, waste water is realized while reducing wastewater toxicity
Qualified discharge, and this method technological process is simple, cost is cheap；
（2）Adsorption column of the present invention, floor space is small, simple to operate, and disposal ability is strong, and usage range is wide, can not only be single
Reason of staying alone waste water, can also support the use with other water treatment facilities, realize the deep removal of heavy metal, thallium contains in adsorption column water outlet
Measure≤0.1 μ g/L, non-secondary pollution generation；
（3）SK-Tl02 type resin sorbents involved in the present invention are the selective absorbents that independent research is prepared, and for weight
The selective removal of thallium optimizes, and has the features such as treating capacity is big, and adsorption capacity is strong, effect stability, and cost is cheap.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits,
Protection scope of the present invention is defined by claims.
Embodiment 1
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 6.2 mg/L, pH 1.1.Will be useless with 10% milk of lime
Water pH is adjusted to 7 or so, adds 0.2% polyaluminium ferrous solution, reaction time 6h, waste water enters through sedimentation centrifuge after reaction
Row separation of solid and liquid, putting-down machine water outlet enter the adsorption column equipped with SK-Tl02 type resin sorbents, and filter mistake is passed through in adsorption column water outlet
Filter, thallium content is 0.06 μ g/L in waste water after filtering, can reuse or directly outer row.
Embodiment 2
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 10 mg/L, pH 0.8.Will with 2 g/L NaOH solutions
Wastewater pH is adjusted to 7 or so, adds 1% bodied ferric sulfate, reaction time 3h, waste water is delivered in filter press and carries out solid-liquid
Separation, filter press water outlet enter electric flocculation removing heavy metals device, and water outlet is filtered, and thallium content is in waste water after filtering
0.08 μ g/L, can reuse or directly outer row.
Embodiment 3
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 4.8 mg/L, pH 1.6.Will be useless with 15% milk of lime
Water pH is adjusted to 7 or so, adds 3% bodied ferric sulfate and the mixture solution of poly-ferric chloride, reaction time 2h, by waste water
It is delivered in gravitational settler and carries out separation of solid and liquid, settler water outlet enters the adsorption column equipped with activated carbon, adsorption column water outlet warp
Filter filters, and thallium content is 0.05 μ g/L in waste water after filtering, can reuse or directly outer row.
Embodiment 4
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 2.3 mg/L, pH 1.4.Will with 2 g/L KOH solutions
Wastewater pH is adjusted to 7 or so, adds 5% polymeric ferrous sulphate solution, reaction time 1h, waste water is delivered in filter press and carried out
Separation of solid and liquid, through nanofiltration membrane, thallium content is 0.12 μ g/L in waste water after filtering, can reuse or directly outer for filter press water outlet
Row.
Embodiment 5
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 1.5 mg/L, pH 2.With 5% milk of lime by waste water
PH is adjusted to 7 or so, adds 0.5% ferrum sulfuricum oxydatum solutum, reaction time 5h, waste water is delivered in gravitational settler and consolidated
Liquid is separated, and settler water outlet enters the adsorption column equipped with SK-Tl02 type resin sorbents, and adsorption column water outlet is filtered,
Thallium content is 0.02 μ g/L in waste water after filtering, can reuse or directly outer row.
Embodiment 6
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 1.5 mg/L, pH 2.With 20% milk of lime by waste water
PH is adjusted to 7 or so, adds 1% liquor ferri trichloridi, reaction time 3h, waste water is delivered in filter and carries out solid-liquid point
From filter water outlet enters the adsorption column equipped with molecular sieve, and adsorption column water outlet is filtered, thallium content in waste water after filtering
, can reuse or directly outer row for 0.03 μ g/L.
Embodiment 7
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 0.5 mg/L, pH 1.6.With 6 g/L Mg (OH)2It is molten
Wastewater pH is adjusted to 7 or so by liquid, is added 3% polymeric ferrous sulphate solution, reaction time 3h, waste water is delivered in filter press
Separation of solid and liquid is carried out, filter press water outlet enters the adsorption column equipped with SK-Tl02 type resin sorbents, and filter is passed through in adsorption column water outlet
Filtering, thallium content is 0.01 μ g/L in waste water after filtering, can reuse or directly outer row.
Embodiment 8
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 4.6 mg/L, pH 1.3.With 2 g/L NaHCO3It is molten
Wastewater pH is adjusted to 7 or so by liquid, is added 2% ferrum sulfuricum oxydatum solutum, reaction time 4h, waste water is delivered in filter press and carried out
Separation of solid and liquid, filter press water outlet enter the adsorption column equipped with polyacrylamide, and adsorption column water outlet is filtered, and are given up after filtering
Thallium content is 0.01 μ g/L in water, can reuse or directly outer row.
Embodiment 9
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 7.5 mg/L, pH 1.1.Will be useless with 30% milk of lime
Water pH is adjusted to 7 or so, adds 5% polymeric aluminum chlorides solution, reaction time 0.5h, waste water is delivered in filter press and carried out
Separation of solid and liquid, filter press water outlet enter the adsorption column equipped with activated carbon and SK-Tl02 type resin sorbents, and adsorption column water outlet is passed through
Filter filters, and thallium content is 0.04 μ g/L in waste water after filtering, can reuse or directly outer row.
Embodiment 10
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 8.2 mg/L, pH 0.9.With carbide slag by wastewater pH
7 or so are adjusted to, adds 1% liquor alumini chloridi, reaction time 5h, waste water, which is delivered in filter, after reaction carries out solid-liquid point
From filter water outlet, which enters, is equipped with kaolinic adsorption column, and adsorption column water outlet is filtered, thallium content in waste water after filtering
, can reuse or directly outer row for 0.15 μ g/L.
Embodiment 11
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 6.4 mg/L, pH 1.4.Will be useless with 15% milk of lime
Water pH is adjusted to 7 or so, adds 2% polymeric ferrous sulphate solution, reaction time 4h, waste water is delivered in gravitational settler
Row separation of solid and liquid, settler water outlet enter activated sludge tank, are separated after 10h is stopped in activated sludge tank through precipitation, supernatant
Middle thallium content is 0.08 μ g/L, can reuse or directly outer row.
Embodiment 12
Certain factory provides a kind of acid waste water containing thallium, and wherein thallium content is 6.4 mg/L, pH 1.4.With 4 g/L Na2CO3It is molten
Wastewater pH is adjusted to 7 or so by liquid, is added 3% polymeric aluminum chlorides solution, reaction time 1h, waste water is delivered in filter press
Separation of solid and liquid is carried out, filter press water outlet enters the adsorption column equipped with chitosan, and adsorption column water outlet is filtered, and is given up after filtering
Thallium content is 0.09 μ g/L in water, can reuse or directly outer row.
Applicant's statement, the method for the invention that the present invention is illustrated by above-described embodiment, but the invention is not limited in
Aforesaid operations step, that is, do not mean that the present invention has to rely on aforesaid operations step and could implemented.The technology of art
Personnel it will be clearly understood that any improvement in the present invention, the addition of equivalence replacement and auxiliary element to raw material selected by the present invention,
Selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (9)
- A kind of 1. method of advanced treating acid waste water containing thallium, it is characterised in that using acid waste water containing thallium as process object, utilize Neutralization precipitation and advanced treating United Technologies are handled, and finally realize that standard water discharge is discharged.
- 2. the method as described in claim 1, it is characterised in that comprise the following steps：（1）PH nertralizers are added into acid waste water containing thallium, wastewater pH is adjusted to neutrality；（2）To step（1）Precipitating reagent is added after neutralization in waste water, then waste water is passed through solid-liquid separating equipment；（3）Supernatant after separation of solid and liquid is subjected to advanced treating, further filtered through filter after processing, standard water discharge discharge.
- 3. method as claimed in claim 2, it is characterised in that step（1）The pH nertralizers are carbide slag, milk of lime, hydrogen One or more in magnesium oxide solution, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or sodium bicarbonate solution；Preferably, pH nertralizers are milk of lime；The concentration 10%~30% of milk of lime；Preferably, the concentration of milk of lime is 10%~25%.
- 4. method as claimed in claim 3, it is characterised in that step（2）The precipitating reagent is polymeric ferrous sulphate solution, polymerization One or more in ferric chloride solution, liquor ferri trichloridi, ferrum sulfuricum oxydatum solutum, liquor alumini chloridi or polymeric aluminum chlorides solution, Precipitating reagent addition is 0.2%~5%, and the reaction time is 0.5h~6h；Preferably, precipitating reagent is polymeric ferrous sulphate solution or polyaluminium ferrous solution；Preferably, the addition of precipitating reagent is 0.5~3%；Preferably, the reaction time is 1h~6h.
- 5. method as claimed in claim 4, it is characterised in that step（2）The solid-liquid separating equipment be gravitational settler, from Heart settler, filter press or filter；Preferably, solid-liquid separating equipment is filter press.
- 6. method as claimed in claim 5, it is characterised in that step（3）The method of the advanced treating is membrane separation process, life Thing method, electric flocculation method or absorption method；Preferably, advanced treating is absorption method.
- 7. method as claimed in claim 6, it is characterised in that the adsorbent selected by the absorption method is activated carbon, molecule One or more in sieve, chitosan, kaolin, polyacrylamide, SK-Tl02 type resin sorbents；Preferably, adsorbent is SK-Tl02 type resin sorbents.
- 8. the method as described in any claim in claim 1-7, it is characterised in that neutralized precipitation and advanced treating connection After closing technical finesse, the μ g/L of thallium content in waste water≤0.1, production technology or qualified discharge can be back to.
- 9. method as claimed in claim 8, it is characterised in that thallium content is 0.5~10mg/L in the acid waste water containing thallium, PH is 0.1~2.
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| CN108395025A (en) * | 2018-05-10 | 2018-08-14 | 长沙矿冶研究院有限责任公司 | A kind of the electric flocculation deep treatment method and electric flocculation device of waste water containing thallium |
| CN108640323A (en) * | 2018-04-02 | 2018-10-12 | 俞祖林 | A kind of processing method of industrial wastewater |
| CN108840422A (en) * | 2018-05-23 | 2018-11-20 | 四川川能环保科技有限公司 | A kind of industrial sewage process method |
| CN110183020A (en) * | 2019-06-06 | 2019-08-30 | 福建兴万祥建设集团有限公司 | A kind of processing method for heavy metal wastewater thereby of digging up mine |
| CN110776184A (en) * | 2019-11-07 | 2020-02-11 | 广东先导稀材股份有限公司 | Advanced treatment method of thallium-containing wastewater |
| CN111039450A (en) * | 2019-12-16 | 2020-04-21 | 北京协同创新研究院 | Integrated runner heavy metal removal system and sewage treatment method |
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| CN115504597A (en) * | 2022-09-19 | 2022-12-23 | 铜陵有色金属集团股份有限公司 | Thallium removal process for pyrite contaminated acid |
| CN119307726A (en) * | 2024-12-17 | 2025-01-14 | 中国科学院过程工程研究所 | A detoxification method and system for treating lithium ore smelting slag based on nanofiltration |
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| CN108640323A (en) * | 2018-04-02 | 2018-10-12 | 俞祖林 | A kind of processing method of industrial wastewater |
| CN108395025A (en) * | 2018-05-10 | 2018-08-14 | 长沙矿冶研究院有限责任公司 | A kind of the electric flocculation deep treatment method and electric flocculation device of waste water containing thallium |
| CN108395025B (en) * | 2018-05-10 | 2024-03-22 | 长沙矿冶研究院有限责任公司 | Electric flocculation advanced treatment method and electric flocculation device for thallium-containing wastewater |
| CN108840422A (en) * | 2018-05-23 | 2018-11-20 | 四川川能环保科技有限公司 | A kind of industrial sewage process method |
| CN110183020B (en) * | 2019-06-06 | 2020-04-24 | 福建兴万祥建设集团有限公司 | Mining heavy metal wastewater treatment method |
| CN110183020A (en) * | 2019-06-06 | 2019-08-30 | 福建兴万祥建设集团有限公司 | A kind of processing method for heavy metal wastewater thereby of digging up mine |
| CN110776184A (en) * | 2019-11-07 | 2020-02-11 | 广东先导稀材股份有限公司 | Advanced treatment method of thallium-containing wastewater |
| CN111039450A (en) * | 2019-12-16 | 2020-04-21 | 北京协同创新研究院 | Integrated runner heavy metal removal system and sewage treatment method |
| CN113636627A (en) * | 2021-10-14 | 2021-11-12 | 北京中关村国际环保产业促进中心有限公司 | Device and method for removing thallium pollution in wastewater |
| CN115504597A (en) * | 2022-09-19 | 2022-12-23 | 铜陵有色金属集团股份有限公司 | Thallium removal process for pyrite contaminated acid |
| CN115504597B (en) * | 2022-09-19 | 2023-11-21 | 安徽铜冠产业技术研究院有限责任公司 | Thallium removal process for pyrite contaminated acid |
| CN119307726A (en) * | 2024-12-17 | 2025-01-14 | 中国科学院过程工程研究所 | A detoxification method and system for treating lithium ore smelting slag based on nanofiltration |
| CN120004449A (en) * | 2025-03-04 | 2025-05-16 | 中南林业科技大学 | A method for treating wastewater containing heavy metals |
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