CN106396199A - Method for removing arsenic in wastewater with combination of compound medicine and sludge adsorption material - Google Patents
Method for removing arsenic in wastewater with combination of compound medicine and sludge adsorption material Download PDFInfo
- Publication number
- CN106396199A CN106396199A CN201611110237.0A CN201611110237A CN106396199A CN 106396199 A CN106396199 A CN 106396199A CN 201611110237 A CN201611110237 A CN 201611110237A CN 106396199 A CN106396199 A CN 106396199A
- Authority
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- China
- Prior art keywords
- arsenic
- waste water
- composite drug
- absorption material
- combination
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 110
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 239000003814 drug Substances 0.000 title claims abstract description 55
- 239000010802 sludge Substances 0.000 title claims abstract description 48
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 52
- 239000002131 composite material Substances 0.000 claims description 45
- 229940079593 drug Drugs 0.000 claims description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 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 9
- 239000000843 powder Substances 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- FGIWMSAVEQNPPQ-UHFFFAOYSA-N arsenic;hydrate Chemical compound O.[As] FGIWMSAVEQNPPQ-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- -1 lamellar Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- FRLCRPUWDUKNGO-UHFFFAOYSA-N methoxyarsonic acid Chemical compound CO[As](O)(O)=O FRLCRPUWDUKNGO-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical class O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 125000001002 arsinoyl group Chemical group O=[AsH2]* 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 210000002356 skeleton Anatomy 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- 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
- C02F1/66—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a method for removing arsenic in wastewater with the combination of a compound medicine and a sludge adsorption material. The method comprises the following steps: adding the compound medicine into wastewater, stirring, adjusting the pH value, and adding the sludge adsorption material for adsorption to remove arsenic in the wastewater, wherein the mole ratio of the compound medicine to the wastewater is (1-50):1. By adopting the method for removing the arsenic in the wastewater with the combination of the compound medicine and the sludge adsorption material, the raw materials are low in price, an arsenic removal process is simple in procedure, economic in operation, convenient to manage and good in arsenic removal effect, the concentration of the arsenic in the wastewater can be effectively reduced, the content of the arsenic in effluent is less than 0.1 mg/L, and emission standards can be met.
Description
Technical field
The invention belongs to water treatment field, especially relate to a kind of composite drug and remove waste water with the combination of sludge absorption material
The method of middle arsenic.
Background technology
Arsenic is a kind of high poison element, can enter the devices such as human liver, kidney, skeleton, hair by food or skin contact
Accumulation in official or tissue, destroys digestive system and nervous system, is studied by the Center for Disease Control (CDC) and international cancer
The authoritative departments such as mechanism (IARC) confirm as first kind carcinogen.Arsenic also has genetoxic, belongs to World Health Organization (WHO) (WHO)
Priority pollutants.Arsenic in water body derives from nature geological activity (as volcanic eruption, rocky erosion etc.), and mankind's life
Product activity is (as the exploitation containing arsenide, smelting, the combustion of the large-scale application of arsenic material, the exploitation of non-ferrous metal and smelting, coal
Burn etc.).Wherein, the discharge containing arsenic Industrial " three Waste ", particularly mining activities are the main causes of water body arsenic pollution.It is estimated that
The whole world there are about 120,000 tons of arsenic every year and is drained in water body so that the arsenic pollution in water body becomes a global problem.At present, Australia
Big Leah, Canada, the U.S., the state such as Japanese and Argentinian all occur in that arseniasiss event, and China arsenic pollution is also in recent years
Now concentrate outburst situation, successively on Guizhou, Hunan, Guangxi, Yunnan, Henan and Jiangsu and other places, arsenic pollution event occurs.Due to arsenic
Pollution has high toxicity, high stability, is difficult to administer and has the reasons such as irreversibility, many states to the destruction of ecological environment
Family and World Health Organization (WHO) have all formulated strict standard to the content of arsenic in waste discharge.As can be seen here, arsenic pollution is seriously endangered
Evil human health and whole ecological environment, develop efficient, practical waste water arsenic removal technology very urgent.
Arsenic in waste water mainly has organo-arsenic and inorganic arsenic, and inorganic arsenic is mainly with Inorganic arsenates (As (V)) and arsenious acid
Presented in salt (As (III)), the toxicity of wherein trivalent arsenic ion pair cell is far above pentavalent arsenic, is the pass of waste water arsenic removal
Key.
The arsenic removal technology of domestic and foreign literature report has at present：The sedimentation method, membrane processing method, absorption method, bioanalysises, ion are handed over
Change method, oxidizing process, extraction, electrocoagulation etc..Any of the above method has a certain degree of removal to arsenic in water, but has
Each different applicable elements and pluses and minuses.Sedimentation method arsenic removal mainly adopts iron salt or aluminium salt, with As (V), flocculation sediment occurs, should
Technology is more perfect, application relatively broad, but it process after can produce a large amount of waste residues, cause secondary pollution.Membrane processing method master
Will be by acting on realization every filter (sieving), but the membrane aperture of independent micro-filtration membrane is too big, can only remove particle form from water
Arsenic, can not retain to deliquescent or colloid arsenic, generally combine with coagulation technology.The reverse osmosiss and nanofiltration removal effect to arsenic
Preferably, but equipment and operating technology are had high demands, operation and maintenance cost is higher, limit the popularization and application of high pressure membrane technology.
Bioanalysises mainly using microorganism or plant to the absorption of arsenic, reduction arsenic concentration of accumulating or be converted, but microorganism is to peripheral edge ring
The requirement in border is very strict.Ion exchange can reach 99% to the clearance of arsenic, but is done by sulfate radical, chlorine and other aniones
Disturb, and regenerated liquid middle and high concentration arsenic is also an environmental problem.Electrocoagulation using aluminum or ferrum as electrode, using electrolytic process
Middle formation Al3+And Fe3+Coagulation, arsenic is transferred to solid phase from liquid phase, realizes solid-liquid separation arsenic removal.But this technology electric energy
Consume big, electrode is easily passivated.Extracting process, due to its own feature, there is presently no the report for industrial production wastewater arsenic removal
Road.Because the toxicity of As (III) and mobility are stronger than As (V), in water, the main arsenite with nonionic state exists, and is one
Plant hydroaropic substance, above-mentioned most methods are poor to the removal effect of As in water (III), and they are mainly used to As in eliminating water
(V).As (III) can be oxidized to As (V) by oxidant by chemical oxidization method, but can only realize arsenic valency when this process is used alone
The conversion of state is it is impossible to reach the purpose of thorough arsenic removal.Therefore, during arsenic removal, typically first adopt oxidant that As (III) is pre-
It is oxidized to As (V), the processes such as precipitation, absorption of passing through afterwards are realized removing.
Absorption method is the bigger serface being provided using adsorbent, by stronger affinity between arsenic pollution thing and adsorbent
Reach the purpose purifying arsenic removal.Comparatively speaking, absorption method is simple, and removal effect is good, and adsorbing material wide material sources, valency
Lattice are cheap, it has also become study hotspot.The active charcoal of conventional adsorbent, activated alumina etc..Though these materials have higher
Absorbability, but expensive, and usage cycles are short, and this kind of material mostly is powder, easily cause at sewage in processing procedure
The problems such as reason system jams.For reduces cost, economize on resources, reach the purpose of the treatment of wastes with processes of wastes against one another, people are constantly to garbage exhibition
Open research, develop new adsorbent.Waterworks sludge is a kind of garbage producing in water treatment procedure, contains in such mud
A large amount of hydroxide such as ferrum, aluminum, and the oxide such as ferrum, aluminum has good absorption and sedimentation function to arsenic.With waterworks sludge it is
Raw material, through granule, lamellar, powder or the granular adsorption material surface microporous structure that series of process processes such as fires
There is very strong absorbability, and ferrum, aluminum oxide are contained in adsorbing material surface, can effectively be combined with arsenic.Using this dirt
The research of mud adsorbing material Adsorption arsenic in waste water is also rarely reported.In view of absorption method is better than As to the absorbability of As (V)
(III), can be combined with oxidant applying using adsorbing material, first As (III) is oxidized to As (V), be greatly improved mud
The Adsorption ability to arsenic for the adsorbing material.
Content of the invention
In view of this, it is contemplated that proposing the side of a kind of composite drug and sludge absorption material combination removal arsenic in waste water
Method, removes arsenic in waste water jointly with the sludge absorption material joint Combined ferrate medicament that purification plant sludge is prepared for raw material
A kind of economic, efficient method, this method reduces the expense of waste water arsenic removal it is achieved that the purpose of twice laid.
For reaching above-mentioned purpose, the technical scheme is that and be achieved in that：
A kind of method that composite drug removes arsenic in waste water with the combination of sludge absorption material, comprises the steps：To waste water
In add composite drug after be stirred, adjust pH value after carry out hydrolysis, be subsequently adding sludge absorption material and adsorbed,
Remove the arsenic in waste water；Wherein, described composite drug and the mol ratio of arsenic in waste water are 1-50:1.
Preferably, described composite drug and the mol ratio of arsenic in waste water are 1-10:1.
Further, the time of described whipping step is 5-120min；The pH value of described regulation pH value step is 4-9；
The time of described adsorption step is 30-120min；The temperature of described adsorption step is 15-35 DEG C.
Preferably, the time of described whipping step is 10-60min；The pH value of described regulation pH value step is 5-7；
The time of described adsorption step is 30-60min；The temperature of described adsorption step is 15-35 DEG C.
Further, described composite drug is obtained by the method comprising the steps：In the basic conditions, to hypochlorite
Iron nitrate solution is added, controlling reaction temperature is 50-65 DEG C, response time 10-60min obtains Fe after reaction in solution6+Dense
Spend the composite drug for 0.05-0.2mol/L；Wherein, the effective chlorine in hypochlorite solutions and the mol ratio of iron nitrate solution are
5-20：1.
Further, in described hypochlorite solutions, the concentration of effective chlorine is 0.8-1.5mol/L；Described hypochlorite
Solution is liquor natrii hypochloritises or calcium hypochlorite solution；The concentration of described iron nitrate solution is 0.14-0.32mol/L；Described
Composite drug in Fe6+Concentration be 0.08-0.16mol/L.
Further, described sludge absorption material is obtained by the method comprising the steps：Using water treatment plant iron content, aluminum
Mud and clay in parts by weight 1:0.1-10 prepares slabbing, powder or granular adsorbing material, after natural air drying,
0.5-1h is dried under the conditions of 105 DEG C, then preheats 10-30min, 900-1100 DEG C of roasting 10-40min molding at 300 DEG C, obtain final product
Described sludge absorption material.
Further, the proportioning of described water treatment plant's iron content, the mud of aluminum and clay is 1:1-5.
Further, when in described calcination stepses, fire box temperature is below 500 DEG C, temperature rate≤5 DEG C/min, burner hearth
When temperature is more than 500 DEG C, temperature rate≤10 DEG C/min.
Further, the grain size of described sludge absorption material is 0.001-5mm.
Arsenic in waste water of the present invention includes inorganic arsenic and organo-arsenic, and wherein inorganic arsenic includes trivalent arsenic and pentavalent
Arsenic.In course of reaction, after first adopting Combined ferrate medicament (i.e. composite drug) oxidation reaction, adjust pH value, after hydrolysis
Enter back into and in adsorption tank, adopt sludge absorption material further Adsorption arsenic, the discharge of wastewater after absorption；Can also be by oxygen
Change reaction and adsorption reaction is placed in same reaction tank and carries out.
The ultimate principle of the present invention is：Using Combined ferrate medicament, the organo-arsenic in waste water and trivalent arsenic are oxidized to
Pentavalent arsenic, the reduction product Fe of ferrate simultaneously3+Produce precipitation with As effect, then adopt sludge absorption material to inhale further
The remaining pentavalent arsenic of attached removal, is finally reached the arsenic removal purpose of highly effective and safe.Ferrate has higher redox potential,
It is 2.2V under acid condition, is 0.72V under alkalescence condition, therefore oxidation can be occurred anti-with the organo-arsenic in water or trivalent arsenic
Should.Combined ferrate medicament aoxidizes the final product Fe of arsenic removal3+Can precipitate with arsenic acid salt formation, and Fe3+Hydrolyzate meeting
Form the hydrated complexes of various forms, with the As (V) in solution, ligand exchange, arsenic ion in absorption water occur.Through compound
Arsenic-containing waste water after the oxidation of ferrate medicament enters adsorption tank, and this adsorption tank is with the mud of water treatment plant's iron content, the preparation of aluminum mud
Adsorbing material is adsorbent, and this adsorbent has certain gap structure, and the metal-oxides such as a certain amount of ferrum, aluminum are contained on surface
Point.Part ferrum, aluminum oxide are converted into ferrum, aluminium hydroxide through hydrolysis in aqueous, and ferrum, aluminium hydroxide are through complexation
There is ligand exchange with the As (V) in solution in effect, and the ferrum on mud adsorbent surface, aluminum oxide are also combined life with arsenic
Become M (H2AsO4)0、M(HAsO4)-、M(HAsO4)2-Deng material (M represents Fe or Al), so that sludge absorption material has to arsenic
Stronger adsorption.
Adsorption step completes in adsorption tank, and adsorbing material can be fixed bed or fluid bed.Course of reaction
In, oxidation reaction and adsorption reaction can carry out it is also possible to carry out in adsorption tank simultaneously respectively in two ponds.
With respect to prior art, composite drug of the present invention removes the side of arsenic in waste water with the combination of sludge absorption material
Method has the advantage that：
The method that composite drug of the present invention removes arsenic in waste water with the combination of sludge absorption material, raw materials valency
Lattice are cheap, and arsenic removal process flow process is simple, operation economy, convenient management, effect of removing arsenic are good, can effectively reduce arsenic in arsenic-containing waste water
Concentration, go out Water jet cleaning be less than 0.1mg/L, reach discharge standard.The present invention all has to organo-arsenic and inorganic arsenic and preferably goes
Except effect, and there is changing waste into resources utilize function.
Brief description
Fig. 1 is the flow chart of the method that composite drug removes arsenic in waste water with the combination of sludge absorption material.
Specific embodiment
In addition to being defined, in following examples technical term used have universal with those skilled in the art of the invention
The identical meanings understanding.Test reagent used in following examples, if no special instructions, is routine biochemistry reagent；Described
Experimental technique, if no special instructions, is conventional method.
To describe the present invention with reference to embodiment and accompanying drawing in detail.
Embodiment 1
As shown in figure 1, a kind of method that composite drug removes arsenic in waste water with the combination of sludge absorption material, walk including following
Suddenly：Xiang Shuizhong adds sodium arsenite, is made into the arsenic-containing waste water that initial arsenic concentration is 10mg/L, and waste water first passes through oxidation pond reaction,
Add composite drug in waste water, mole the adding than for 5 of composite drug and arsenic:1, stir 30min, then HCl solution is adjusted
PH value carries out hydrolysis to 6-7, and water outlet enters adsorption tank, is subsequently adding sludge absorption material and carries out adsorbing 60min, absorption
Pond is fixed bed, and water outlet arsenic concentration is 0.04mg/L, reaches discharge standard.
Described composite drug is obtained by the method comprising the steps：To the hypochlorous acid for 1.0mol/L for the effective chlorine density
Add sodium hydroxide solution to prepare alkaline environment in sodium solution, add the iron nitrate solution of 0.2mol/L, described is secondary
In solution of chlorate, effective chlorine and the mol ratio of iron nitrate solution are 5：1, controlling reaction temperature is 60-65 DEG C, the response time
30min, obtains Fe after reaction6+Concentration be 0.14mol/L composite drug.
Described sludge absorption material is obtained by the method comprising the steps：Using water treatment plant's iron content, the mud of aluminum with
Clay in parts by weight 1:2 prepare slabbing, powder or granular adsorbing material, after natural air drying, under the conditions of 105 DEG C
1h is dried, then preheats 20min, 1000 DEG C of roasting 20-30min molding at 300 DEG C, obtain final product described sludge absorption material.
Embodiment 2
A kind of method that composite drug removes arsenic in waste water with the combination of sludge absorption material, comprises the steps：Xiang Shuizhong
Add sodium arsenite and natrium arsenicum, be made into the mixing arsenic waste water that initial arsenic concentration is 12mg/L, waste water first passes through oxidation pond reaction,
Add composite drug in waste water, mole the adding than for 4 of composite drug and arsenic:1, stir 20min, be subsequently adding HCl or
H2SO4Solution adjusts pH value and is hydrolyzed reaction to 6, water outlet entrance adsorption tank, is subsequently adding sludge absorption material and is adsorbed
60min, adsorption tank is fluid bed, and water outlet arsenic concentration is 0.05mg/L, less than 0.1mg/L, reaches discharge standard.
Described composite drug is obtained by the method comprising the steps：To the hypochlorous acid for 1.3mol/L for the effective chlorine density
Potassium hydroxide solution is added to prepare alkaline environment in calcium solution, in described hypochlorite solutions, effective chlorine is molten with ferric nitrate
The mol ratio of liquid is 5.2：1, add the iron nitrate solution of 0.25mol/L, controlling reaction temperature is 60-65 DEG C, the response time
50min, obtains Fe after reaction6+Concentration be 0.16mol/L composite drug.
Described sludge absorption material is obtained by the method comprising the steps：Using water treatment plant's iron content, the mud of aluminum with
Clay in parts by weight 1:4 prepare slabbing, powder or granular adsorbing material, after natural air drying, under the conditions of 105 DEG C
1h is dried, then preheats 30min, 1000 DEG C of roasting 20-30min molding at 300 DEG C, obtain final product described sludge absorption material.
Embodiment 3
A kind of method that composite drug removes arsenic in waste water with the combination of sludge absorption material, comprises the steps：Xiang Shuizhong
Add monomethyl arsenic acid (MMA), be made into the mixing arsenic waste water that initial arsenic concentration is 5mg/L, waste water first passes through adsorption tank reaction (should
Adsorption tank is fluid bed), add composite drug in waste water, composite drug and arsenic mole add ratio for 5:1, stir 40min,
Then adjust pH value and reach 6.5 and be hydrolyzed reaction, water outlet entrance adsorption tank, it is subsequently adding sludge absorption material and adsorbed
60min, adsorption tank is fluid bed, and water outlet arsenic concentration is 0.02mg/L, less than 0.1mg/L, reaches discharge standard.
Described composite drug is obtained by the method comprising the steps：To the hypochlorous acid for 1.1mol/L for the effective chlorine density
Potassium hydroxide solution is added to prepare alkaline environment in sodium solution, in described hypochlorite solutions, effective chlorine is molten with ferric nitrate
The mol ratio of liquid is 6.1：1, add the iron nitrate solution of 0.18mol/L, controlling reaction temperature is 55-60 DEG C, the response time
50-60min, obtains Fe after reaction6+Concentration be 0.11mol/L composite drug.
Described sludge absorption material is obtained by the method comprising the steps：Using water treatment plant's iron content, the mud of aluminum with
Clay in parts by weight 1:3 prepare slabbing, powder or granular adsorbing material, after natural air drying, under the conditions of 105 DEG C
1h is dried, then preheats 30min, 1000 DEG C of roasting 20-30min molding at 300 DEG C, obtain final product described sludge absorption material.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (10)
1. the combination of a kind of composite drug and sludge absorption material remove arsenic in waste water method it is characterised in that：Walk including following
Suddenly：Add in waste water after composite drug and be stirred, carry out hydrolysis after adjusting pH value, be subsequently adding sludge absorption material
Adsorbed, removed the arsenic in waste water；Wherein, described composite drug and the mol ratio of arsenic in waste water are 1-50:1.
2. the method that composite drug according to claim 1 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：Described composite drug is 1-10 with the mol ratio of arsenic in waste water:1.
3. the method that composite drug according to claim 1 and 2 removes arsenic in waste water with the combination of sludge absorption material, it is special
Levy and be：The time of described whipping step is 5-120min；The pH value of described regulation pH value step is 4-9；Described suction
The time of attached step is 30-120min；The temperature of described adsorption step is 15-35 DEG C.
4. the method that composite drug according to claim 3 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：The time of described whipping step is 10-60min；The pH value of described regulation pH value step is 5-7；Described absorption
The time of step is 30-60min；The temperature of described adsorption step is 15-35 DEG C.
5. the method that composite drug according to claim 1 and 2 removes arsenic in waste water with the combination of sludge absorption material, it is special
Levy and be：Described composite drug is obtained by the method comprising the steps：In the basic conditions, add in hypochlorite solutions
Enter iron nitrate solution, controlling reaction temperature is 50-65 DEG C, response time 10-60min obtains Fe after reaction6+Concentration be
The composite drug of 0.05-0.2mol/L；Wherein, the effective chlorine in hypochlorite solutions and the mol ratio of iron nitrate solution are 5-
20：1.
6. the method that composite drug according to claim 5 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：In described hypochlorite solutions, the concentration of effective chlorine is 0.8-1.5mol/L；Described hypochlorite solutions are time chlorine
Acid sodium solution or calcium hypochlorite solution；The concentration of described iron nitrate solution is 0.14-0.32mol/L；Described composite drug
Middle Fe6+Concentration be 0.08-0.16mol/L.
7. the method that composite drug according to claim 1 and 2 removes arsenic in waste water with the combination of sludge absorption material, it is special
Levy and be：Described sludge absorption material is obtained by the method comprising the steps：Using water treatment plant's iron content, the mud of aluminum with viscous
Soil in parts by weight 1:0.1-10 prepares slabbing, powder or granular adsorbing material, after natural air drying, in 105 DEG C of bars
0.5-1h is dried under part, then preheats 10-30min, 900-1100 DEG C of roasting 10-40min molding at 300 DEG C, obtain final product described
Sludge absorption material.
8. the method that composite drug according to claim 7 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：The proportioning of described water treatment plant's iron content, the mud of aluminum and clay is 1:1-5.
9. the method that composite drug according to claim 7 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：When in described calcination stepses, fire box temperature is below 500 DEG C, temperature rate≤5 DEG C/min, fire box temperature is 500
When more than DEG C, temperature rate≤10 DEG C/min.
10. the method that composite drug according to claim 7 removes arsenic in waste water with the combination of sludge absorption material, its feature
It is：The grain size of described sludge absorption material is 0.001-5mm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559354A (en) * | 2009-04-29 | 2009-10-21 | 同济大学 | Preparation method of sludge absorber and applications thereof |
| CN203922894U (en) * | 2014-05-30 | 2014-11-05 | 哈尔滨工程大学 | The device of arsenic in removal water is synchronizeed in a kind of oxidation with absorption |
| CN106007076A (en) * | 2016-07-04 | 2016-10-12 | 赣州有色冶金研究所 | Treatment method of arsenic-containing wastewater in tungsten smelting |
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2016
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|---|---|---|---|---|
| CN101559354A (en) * | 2009-04-29 | 2009-10-21 | 同济大学 | Preparation method of sludge absorber and applications thereof |
| CN203922894U (en) * | 2014-05-30 | 2014-11-05 | 哈尔滨工程大学 | The device of arsenic in removal water is synchronizeed in a kind of oxidation with absorption |
| CN106007076A (en) * | 2016-07-04 | 2016-10-12 | 赣州有色冶金研究所 | Treatment method of arsenic-containing wastewater in tungsten smelting |
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| 林璐等: "不同粒径铁铝泥对砷(Ⅲ)的吸附效果", 《环境科学》 * |
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