CN112808252A - Contaminated acid arsenic removal adsorbent and preparation method and application thereof - Google Patents
Contaminated acid arsenic removal adsorbent and preparation method and application thereof Download PDFInfo
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- CN112808252A CN112808252A CN202011620496.4A CN202011620496A CN112808252A CN 112808252 A CN112808252 A CN 112808252A CN 202011620496 A CN202011620496 A CN 202011620496A CN 112808252 A CN112808252 A CN 112808252A
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- arsenic
- arsenic removal
- pyroantimonate
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 121
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002253 acid Substances 0.000 title claims abstract description 74
- 239000003463 adsorbent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000008346 aqueous phase Substances 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 26
- UCXOJWUKTTTYFB-UHFFFAOYSA-N antimony;heptahydrate Chemical compound O.O.O.O.O.O.O.[Sb].[Sb] UCXOJWUKTTTYFB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000011780 sodium chloride Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000005185 salting out Methods 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 27
- 238000001179 sorption measurement Methods 0.000 claims description 17
- -1 methylhydroxypropyl Chemical group 0.000 claims description 9
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 44
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000009616 inductively coupled plasma Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical class [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
- B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A contaminated acid arsenic removal adsorbent and a preparation method and application thereof belong to the technical field of heavy metal wastewater treatment. The preparation method of the contaminated acid arsenic removal adsorbent comprises the following steps: s1, adding a dispersing agent and a salting-out agent NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A; s2, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent to obtain an oil phase solution B, adding an initiator, stirring at room temperature, and adding pyroantimonate powder to obtain a mixture; s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 50-70 ℃ for reaction for 2-6h, then heating to 80-95 ℃ for reaction for 4-10 h; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with the pyroantimonate. The invention solves the problems of difficult dearsenification from waste acid, high treatment cost, more dangerous waste products, easy secondary pollution, high dearsenification agent dissolution loss rate and the like in the prior art.
Description
Technical Field
The invention relates to a technology in the field of heavy metal wastewater treatment, in particular to a contaminated acid arsenic removal adsorbent and a preparation method and application thereof.
Background
The waste acid is mainly from the hydrometallurgy process of lead, copper, zinc and other heavy metals and the washing and purifying process before the sulfur dioxide flue gas is used for preparing the sulfuric acid. The contaminated acid has complex composition, contains high-concentration sulfuric acid, and also contains various heavy metal (such as arsenic, cadmium, lead, zinc and the like) impurities, fluorine, chlorine, phosphorus and the like. In addition, low-grade ores (such as high-arsenic high-copper ores, high-arsenic high-zinc ores and the like) are leached by adopting high-concentration sulfuric acid and enter a hydrometallurgy process, so that the arsenic content in the waste acid is higher and higher. The arsenic content in the waste acid is high, which is extremely unfavorable for the hydrometallurgy process and also has great harm to the natural environment of human existence. Therefore, the method has important economic value and social significance for removing arsenic from the waste acid.
At present, the methods for removing arsenic from waste acid mainly comprise lime neutralization precipitation, iron salt precipitation, sulfide precipitation and the like, and the lime neutralization precipitation is generally adopted in industry. Lime neutralization precipitation and iron salt precipitation: the purpose of removing arsenic is achieved by reacting arsenate (or arsenite) in the solution with calcium ions or iron ions under the condition that the pH value is 3-6 to generate calcium arsenate or ferric arsenate compounds. The lime neutralization precipitation method is used for arsenic removal of waste acid, is a commonly used technology in industry, but consumes a large amount of alkali liquor raw materials, and can generate high-concentration salt-containing wastewater to cause secondary pollution; meanwhile, the waste of sulfuric acid resources is also caused. In addition, the waste acid is dearsenified by a neutralization precipitation method, and a large amount of arsenic-containing solid waste is generated, is unstable and is easy to cause secondary pollution. Sulfide precipitation method: forming insoluble sulfide precipitate by using sulfide ions and arsenic ions to remove arsenic; however, adding vulcanizing agents (such as sodium sulfide and potassium sulfide) into the arsenic-containing sewage can generate a large amount of toxic gas containing hydrogen sulfide, which is not beneficial to industrial production.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
The invention provides a contaminated acid arsenic removal adsorbent, a preparation method and application thereof aiming at the defects in the prior art, and solves the problems that in the prior art, arsenic removal from contaminated acid is difficult, treatment cost is high, more dangerous waste products are generated, secondary pollution is easily caused, the arsenic removal agent dissolution rate is high, and the like.
The invention relates to a preparation method of a contaminated acid arsenic removal adsorbent, which comprises the following steps:
s1, adding a dispersing agent and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent and the salting-out agent NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersant is 0.5-3.0%, and the weight proportion of the salting-out agent NaCl is 5-15%;
s2, uniformly mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature until the initiator is completely dissolved, and then adding pyroantimonate powder into the initiator to obtain a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 50-70 ℃ for reaction for 2-6h, then heating to 80-95 ℃ for reaction for 4-10 h; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with the pyroantimonate.
The pyroantimonate is at least one of sodium pyroantimonate, potassium pyroantimonate and ammonium pyroantimonate; the solid-to-liquid ratio of the pyroantimonate powder oil phase solution B is 0.02 g/L-0.5 g/L.
In step S2, the polymer monomer is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate.
In step S2, the dispersant is at least one of PVA-1000, PVA-6000, PVA-10000, PEG-200, PEG-600, PEG-1000, hydroxymethyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose.
In step S2, the crosslinking agent is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate, and allyl isocyanurate.
In step S2, the initiator is benzoyl peroxide and/or azobisisobutyronitrile.
In step S2, the pore-forming agent is at least one of toluene, isooctane, aviation gasoline, and n-heptane.
In some technical schemes, the weight ratio of the monomer to the cross-linking agent is 1:3-3:1, the weight ratio of the monomer to the cross-linking agent to the pore-forming agent is 2:1-1:2, and the addition amount of the initiator is 0.1-2% of the weight of the oil phase solution B.
The treatment process of the arsenic-containing waste acid wastewater by adopting the waste acid arsenic removal adsorbent comprises the following steps: firstly, adsorbing arsenic-containing waste acid wastewater by using an adsorption column containing a waste acid arsenic removal adsorbent to form an arsenic-containing adsorbent and arsenic removal wastewater; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenide from the arsenic-rich solution.
Technical effects
Compared with the prior art, the invention has the following technical effects:
through an in-situ polymerization method, a dearsenization agent pyroantimonate is hybridized into a pore channel of a high polymer material to prepare a high polymer-based dearsenization adsorbent, and then the high polymer-based dearsenization adsorbent is filled into an adsorption column and can be repeatedly used for removing arsenic in arsenic-containing polluted acid through adsorption and desorption; solves the problems of difficult dearsenization from waste acid, high treatment cost, more dangerous waste products, easy secondary pollution, high dissolution loss rate of dearsenization agent, easy loss of active components and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an arsenic removal adsorbent for contaminated acid according to an embodiment of the present invention;
FIG. 2 is a process diagram of the treatment of arsenic-containing waste acid wastewater in the embodiment of the invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description. The experimental procedures, in which specific conditions are not specified in the examples, were carried out according to the conventional methods and conditions.
Example 1
As shown in fig. 1, the process for preparing the contaminated acid arsenic removal adsorbent in this example is as follows:
s1, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature until the dispersing agent and the NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersant is 3.0 percent, and the weight proportion of NaCl is 10.0 percent;
s2, mixing the components in a weight ratio of 1: 3: 4, mixing the polymer monomer, the cross-linking agent and the pore-foaming agent to obtain an oil phase solution B, adding an initiator accounting for 6 percent of the weight of the oil phase solution B, and stirring at room temperature until the initiator is completely dissolved; then adding sodium pyroantimonate powder according to the solid-to-liquid ratio of 0.2g/L of the pyroantimonate powder to the oil phase solution B to prepare a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2 according to a certain proportion, and stirring at the rotating speed of 500rpm to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃ for reaction for 3h, then heating to 85 ℃ for reaction for 8 h; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with sodium pyroantimonate.
The treatment process of the arsenic-containing waste acid wastewater (the arsenic-containing waste acid wastewater is shown in table 1 below) by using the embodiment is shown in fig. 2, an adsorption column of an arsenic-removing adsorbent containing waste acid is firstly adopted to adsorb the arsenic-containing waste acid wastewater, and the temperature of the adsorption column is controlled to be 45 ℃ in the adsorption process to form the arsenic-containing adsorbent and arsenic-removing wastewater; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenic compounds such as arsenic trioxide from the arsenic-rich solution. After the arsenic-containing adsorbent is desorbed, if the arsenic content does not reach the optimal standard for preparing arsenide, the adsorption and desorption can be repeated.
And measuring the arsenic content in the arsenic-removing wastewater by adopting ICP (inductively coupled plasma), and calculating the arsenic removal rate.
TABLE 1 ingredient table of arsenic-containing waste acid wastewater
| Name (R) | Sulfuric acid (g/L) | Arsenic (g/L) | Copper (g/L) | Nickel (g/L) |
| Arsenic-containing waste acid wastewater | 185 | 13.4 | 46.8 | 10.5 |
Example 2
As shown in fig. 1, the process for preparing the contaminated acid arsenic removal adsorbent in this example is as follows:
s1, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature until the dispersing agent and the NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersing agent is 2 percent, and the weight proportion of NaCl is 8 percent;
s2, mixing the components in a weight ratio of 1: 3: 2, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent to obtain an oil phase solution B, adding an initiator accounting for 4 wt% of the oil phase solution B, and stirring at room temperature until the initiator is completely dissolved; then adding sodium pyroantimonate powder according to the solid-to-liquid ratio of 0.35g/L of the sodium pyroantimonate powder to the oil phase solution B to prepare a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2 according to a certain proportion, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 55 ℃ for reaction for 3h, then heating to 90 ℃ for reaction for 6 h; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with sodium pyroantimonate.
The treatment process of the arsenic-containing waste acid wastewater (the arsenic-containing waste acid wastewater is shown in table 2 below) by using the embodiment is shown in fig. 2, an adsorption column of an arsenic-removing adsorbent containing waste acid is firstly adopted to adsorb the arsenic-containing waste acid wastewater, and the temperature of the adsorption column is controlled to be 55 ℃ in the adsorption process, so that the arsenic-containing adsorbent and arsenic-removing wastewater are formed; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenide from the arsenic-rich solution.
And measuring the arsenic content in the arsenic-removing wastewater by adopting ICP (inductively coupled plasma), and calculating the arsenic removal rate.
TABLE 2 ingredient table of arsenic-containing waste acid wastewater
| Name (R) | Sulfuric acid (g/L) | Arsenic (g/L) | Copper (g/L) | Nickel (g/L) |
| Arsenic-containing waste acid wastewater | 185 | 13.4 | 46.8 | 10.5 |
Example 3
As shown in fig. 1, the process for preparing the contaminated acid arsenic removal adsorbent in this example is as follows:
s1, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature until the dispersing agent and the NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersing agent is 3 percent, and the weight proportion of NaCl is 12 percent;
s2, according to the weight ratio of 3: 1:3, mixing the polymer monomer, the cross-linking agent and the pore-foaming agent to obtain an oil phase solution B, adding an initiator accounting for 8 percent of the weight of the oil phase solution B, and stirring at room temperature until the initiator is completely dissolved; then adding potassium pyroantimonate powder according to the solid-to-liquid ratio of 0.5g/L of the potassium pyroantimonate powder to the oil phase solution B to prepare a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2 according to a certain proportion, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 55 ℃ for reaction for 6h, and then heating to 80 ℃ for reaction for 6 h; and finally, cooling and washing to obtain the polymer-based de-arsenic adsorbent loaded with the potassium pyroantimonate.
The treatment process of the arsenic-containing waste acid wastewater (the arsenic-containing waste acid wastewater is shown in table 3 below) by using the embodiment is shown in fig. 2, an adsorption column of an arsenic-removing adsorbent containing waste acid is firstly adopted to adsorb the arsenic-containing waste acid wastewater, and the temperature of the adsorption column is controlled to be 55 ℃ in the adsorption process, so that the arsenic-containing adsorbent and arsenic-removing wastewater are formed; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenide from the arsenic-rich solution.
And measuring the arsenic content in the arsenic-removing wastewater by adopting ICP (inductively coupled plasma), and calculating the arsenic removal rate.
TABLE 3 ingredient table of arsenic-containing waste acid wastewater
| Name (R) | Sulfuric acid (g/L) | Arsenic (g/L) | Copper (g/L) | Nickel (g/L) |
| Arsenic-containing waste acid wastewater | 185 | 13.4 | 46.8 | 10.5 |
Example 4
As shown in fig. 1, the process for preparing the contaminated acid arsenic removal adsorbent in this example is as follows:
s1, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature until the dispersing agent and the NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersing agent is 2 percent, and the weight proportion of NaCl is 8 percent;
s2, according to the weight ratio of 2: 1:3, mixing the polymer monomer, the cross-linking agent and the pore-foaming agent to obtain an oil phase solution B, adding an initiator accounting for 3 percent of the weight of the oil phase solution B, and stirring at room temperature until the initiator is completely dissolved; then adding mixed powder of ammonium pyroantimonate and sodium pyroantimonate according to the solid-to-liquid ratio of 0.22g/L of the pyroantimonate powder to the oil phase solution B to prepare a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2 according to a certain proportion, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃, reacting for 4 hours, then heating to 95 ℃, and reacting for 8 hours; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with the pyroantimonate.
The treatment process of the arsenic-containing waste acid wastewater (the arsenic-containing waste acid wastewater is shown in table 4 below) by using the embodiment is shown in fig. 2, an adsorption column of an arsenic-removing adsorbent containing waste acid is firstly adopted to adsorb the arsenic-containing waste acid wastewater, and the temperature of the adsorption column is controlled to be 45 ℃ in the adsorption process to form the arsenic-containing adsorbent and arsenic-removing wastewater; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenide from the arsenic-rich solution.
And measuring the arsenic content in the arsenic-removing wastewater by adopting ICP (inductively coupled plasma), and calculating the arsenic removal rate.
TABLE 4 ingredient table of arsenic-containing waste acid wastewater
| Name (R) | Sulfuric acid (g/L) | Arsenic (g/L) | Copper (g/L) | Nickel (g/L) |
| Arsenic-containing waste acid wastewater | 185 | 13.4 | 46.8 | 10.5 |
The results of the arsenic-containing waste acid wastewater treatment in examples 1 to 4 were examined to obtain a water quality condition summary table shown in Table 5.
TABLE 5 summary table of effluent quality of arsenic removal from contaminated acid
| Item | Sulfuric acid (g/L) | Arsenic (g/L) | Copper (g/L) | Nickel (g/L) | Arsenic desorption rate (%) |
| Arsenic-containing waste acid wastewater | 185 | 13.4 | 46.8 | 10.5 | / |
| Example 1 dearsenification wastewater | 176 | 0.12 | 44.3 | 9.8 | 99.1 |
| Example 2 dearsenification wastewater | 167 | 0.23 | 43.8 | 9.5 | 98.3 |
| Example 3 dearsenification wastewater | 182 | 0.72 | 45.2 | 10.2 | 94.6 |
| Example 4 dearsenification wastewater | 163 | 0.83 | 43.5 | 9.1 | 93.8 |
Through the embodiment, the invention has the advantages that the arsenic removal rate is high, and the sulfuric acid, copper and nickel can be efficiently recovered after arsenic removal.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The contaminated acid arsenic removal adsorbent is characterized by being a polymer-based arsenic removal adsorbent loaded with pyroantimonate.
2. The preparation method of the contaminated acid arsenic removal adsorbent is characterized by comprising the following steps:
s1, adding a dispersing agent and a salting-out agent NaCl into deionized water, and stirring at room temperature until the dispersing agent and the salting-out agent NaCl are completely dissolved to obtain an aqueous phase solution A; in the aqueous phase solution A, the weight proportion of the dispersant is 0.5-3.0%, and the weight proportion of the salting-out agent NaCl is 5-15%;
s2, uniformly mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature until the initiator is completely dissolved, and then adding pyroantimonate powder to obtain a mixture;
s3, adding the aqueous phase solution A prepared in the step S1 into the mixture prepared in the step S2, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 50-70 ℃ for reaction for 2-6h, then heating to 80-95 ℃ for reaction for 4-10 h; and finally, cooling and washing to obtain the high-molecular-base arsenic removal adsorbent loaded with the pyroantimonate.
3. The method for preparing the arsenic-removing adsorbent for the contaminated acid according to claim 2, wherein the pyroantimonate is at least one of sodium pyroantimonate, potassium pyroantimonate and ammonium pyroantimonate; the solid-to-liquid ratio of the pyroantimonate powder oil phase solution B is 0.02 g/L-0.5 g/L.
4. The method for preparing the arsenic removing adsorbent according to claim 2, wherein in step S2, the polymer monomer is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate and butyl methacrylate.
5. The method for preparing the contaminated acid arsenic removal adsorbent according to claim 2, wherein in step S2, the dispersant is at least one of PVA-1000, PVA-6000, PVA-10000, PEG-200, PEG-600, PEG-1000, hydroxymethyl cellulose, hydroxyethyl cellulose, and methylhydroxypropyl cellulose.
6. The method for preparing the contaminated acid arsenic removal adsorbent according to claim 2, wherein in step S2, the crosslinking agent is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate, and allyl isocyanurate.
7. The method for preparing the contaminated acid arsenic removal adsorbent according to claim 2, wherein in step S2, the initiator is benzoyl peroxide and/or azobisisobutyronitrile.
8. The method for preparing the contaminated acid arsenic removal adsorbent according to claim 2, wherein in step S2, the pore-forming agent is at least one of toluene, isooctane, aviation gasoline and n-heptane.
9. The preparation method of the contaminated acid arsenic removal adsorbent according to claim 2, wherein the weight ratio of the monomer to the cross-linking agent is 1:3-3:1, the weight ratio of the monomer to the cross-linking agent to the pore-forming agent is 2:1-1:2, and the addition amount of the initiator is 0.1% -2% of the weight of the oil phase solution B.
10. The application of a contaminated acid arsenic removal adsorbent in the arsenic-containing contaminated acid wastewater treatment process comprises the steps of firstly, adsorbing arsenic-containing contaminated acid wastewater by using an adsorption column containing the contaminated acid arsenic removal adsorbent to form an arsenic-containing adsorbent and arsenic removal wastewater; recovering acid and other high-value metals from the arsenic-removed wastewater; and introducing alkali liquor to desorb and regenerate the arsenic-containing adsorbent to form an arsenic-rich solution, and preparing arsenide from the arsenic-rich solution.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN104973710A (en) * | 2014-04-10 | 2015-10-14 | 中国科学院生态环境研究中心 | Method of treating high-concentration arsenic and cadmium in acidic waste water with granular titanium dioxide |
| CN105347544A (en) * | 2015-10-31 | 2016-02-24 | 江西铜业股份有限公司 | Method for precipitating and separating arsenic from waste acid wastewater |
| CN108176345A (en) * | 2018-01-04 | 2018-06-19 | 清华大学 | The application of particulate form MnSb sorbent preparation methods and product and its removal radioactivity Sr, Co and Ag |
| CN111138235A (en) * | 2020-01-13 | 2020-05-12 | 中国农业大学 | Salt ion and pH dual-sensitive high-molecular saline-alkali soil sustained and controlled release membrane material and preparation method thereof |
-
2020
- 2020-12-30 CN CN202011620496.4A patent/CN112808252A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN104973710A (en) * | 2014-04-10 | 2015-10-14 | 中国科学院生态环境研究中心 | Method of treating high-concentration arsenic and cadmium in acidic waste water with granular titanium dioxide |
| CN105347544A (en) * | 2015-10-31 | 2016-02-24 | 江西铜业股份有限公司 | Method for precipitating and separating arsenic from waste acid wastewater |
| CN108176345A (en) * | 2018-01-04 | 2018-06-19 | 清华大学 | The application of particulate form MnSb sorbent preparation methods and product and its removal radioactivity Sr, Co and Ag |
| CN111138235A (en) * | 2020-01-13 | 2020-05-12 | 中国农业大学 | Salt ion and pH dual-sensitive high-molecular saline-alkali soil sustained and controlled release membrane material and preparation method thereof |
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