CN109107550A - A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling - Google Patents
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling Download PDFInfo
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- CN109107550A CN109107550A CN201810859843.5A CN201810859843A CN109107550A CN 109107550 A CN109107550 A CN 109107550A CN 201810859843 A CN201810859843 A CN 201810859843A CN 109107550 A CN109107550 A CN 109107550A
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- arsenic
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 155
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 148
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000004064 recycling Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000007420 reactivation Effects 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000605 extraction Methods 0.000 claims abstract description 42
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 40
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- JPWGUOFOCAZONZ-UHFFFAOYSA-N heptan-1-amine;hydrobromide Chemical class Br.CCCCCCCN JPWGUOFOCAZONZ-UHFFFAOYSA-N 0.000 claims description 4
- ZLSVALLKHLKICA-UHFFFAOYSA-N hexan-1-amine;hydrobromide Chemical class [Br-].CCCCCC[NH3+] ZLSVALLKHLKICA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- FECKHSTWGKTQAN-UHFFFAOYSA-N pentan-1-amine;hydrobromide Chemical compound [Br-].CCCCC[NH3+] FECKHSTWGKTQAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000002734 clay mineral Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- IPUIVTFLFRYUBR-UHFFFAOYSA-N nonylazanium bromide Chemical class [Br-].C(CCCCCCCC)[NH3+] IPUIVTFLFRYUBR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003408 phase transfer catalysis Methods 0.000 claims 2
- 239000000284 extract Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 24
- 239000011651 chromium Substances 0.000 description 23
- 229910052804 chromium Inorganic materials 0.000 description 23
- 229910052742 iron Inorganic materials 0.000 description 21
- 239000011133 lead Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 229910052793 cadmium Inorganic materials 0.000 description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 12
- 239000007767 bonding agent Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RIPUKAXZALFIMA-UHFFFAOYSA-N decan-1-amine;hydrobromide Chemical class [Br-].CCCCCCCCCC[NH3+] RIPUKAXZALFIMA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910017251 AsO4 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 125000001870 arsonato group Chemical group O=[As]([O-])([O-])[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- MVYQJCPZZBFMLF-UHFFFAOYSA-N hydron;propan-1-amine;bromide Chemical compound [Br-].CCC[NH3+] MVYQJCPZZBFMLF-UHFFFAOYSA-N 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/001—Preparation involving a solvent-solvent extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to the methods of a kind of adsorbent reactivation of arsenic pollution and arsenic recycling, belong to environmental technology field.The adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I by the present invention, it adds metallic bond and is passed through carbon dioxide gas, heating is forced into the supercriticality of carbon dioxide, the reproducing adsorbent and extraction product that 5 ~ 90min of contact extraction is parsed, wherein the temperature of CO 2 supercritical state is 35 ~ 85 DEG C, and pressure is 7.5 ~ 50MPa；Extraction product, water, excessive oxidant are added to be uniformly mixed in high-temperature high-pressure reaction kettle II and obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II and reaches water supercriticality, and it reacts 3 ~ 35min and obtains reaction product system, wherein the temperature of supercriticality is 375 ~ 600 DEG C, and pressure is 22.5 ~ 50Mpa.The method of the present invention extracts arsenic and heavy metal ion mildly using supercritical carbon dioxide to parse the adsorbent of pollution, and arsenic is recycled in the form of arsenic trioxide.
Description
Technical field
The present invention relates to the methods of a kind of adsorbent reactivation of arsenic pollution and arsenic recycling, belong to environmental technology field.
Background technique
Arsenic and its compound are common environmental contaminants, there is the carcinogen of biggish toxicity, if its uncontrolled pole
It easily pollutes the environment, and pollution is also difficult to eliminate once being formed, by the Center for Disease Control and country's anti-cancer research
Mechanism is determined as first kind carcinogenic substance.Arsenic can enter human body by food chain or the surface water, underground water, and the serious damage mankind are strong
Health.Arsenic removal measure at present be mainly summarised as absorption method, Coagulation Method, direct precipitation method, ion-exchange, extraction, hyperfiltration,
Bioanalysis etc..In these methods, absorption method has the characteristics that efficient, economical, convenient and easy, is with the most local
Method.And the regeneration for adsorbent material, it can reuse and increase economic efficiency.The arsenic resource resource important as one kind,
It is necessary for the recycling of arsenic during adsorbent reactivation.
A kind of innoxious and parsing of activated alumina adsorbents containing arsenic is disclosed in Chinese patent CN 102068970A again
Raw technology, is desorbed using sodium hydroxide solution, and portland cement solidification is then added, realizes the regeneration of aluminium oxide, but does not have
There is effective recycling arsenic resource.A kind of absorption of iron modified red mud arsenic-removing is disclosed in Chinese patent CN101176840B to remember to apply
Method prepares adsorbent using red mud and iron chloride as raw material, realizes and regenerates also with sodium hydroxide, and there is no the processing to arsenic
It is further elaborated.A kind of preparation of arsenic adsorbent is disclosed in Chinese patent CN102698703B and handles the side of waste water
Method after adsorbent completes absorption, successively utilizes sulfuric acid and calcination processing, regains adsorbent.In above-mentioned technical method, all
The regeneration of adsorbent can be effectively realized, but there is no recycling arsenic, causes the waste of arsenic resource.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides the methods of a kind of adsorbent reactivation of arsenic pollution and arsenic recycling, originally
Inventive method can reduce the consumption of reagent and material, and mild quickly purification adsorbent containing arsenic extracts the adsorbent of arsenic pollution
In arsenic and heavy metal ion；Meanwhile arsenic resource is recycled in the form of arsenic trioxide, to realize the harmless of the adsorbent containing arsenic
Change processing and resource utilization.
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, adds metallic bond and is passed through carbon dioxide gas
Body, heating are forced into the supercriticality of carbon dioxide, and the reproducing adsorbent and extraction that 5 ~ 90min of contact extraction is parsed produce
Object, wherein the temperature of CO 2 supercritical state is 35 ~ 85 DEG C, and pressure is 7.5 ~ 50Mpa；Adsorbent is carbon adsorbent, metal
Oxide adsorbent and/or mineral adsorbent；Heavy metal ion containing pollution adsorbent in the adsorbent of arsenic pollution；
(2) extraction product, water, the excessive oxidant of step (1) are added to be uniformly mixed in high-temperature high-pressure reaction kettle II and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle II and reaches water in confined conditions
Supercriticality, and react 3 ~ 35min and obtain reaction product system, wherein the temperature of supercriticality is 375 ~ 600 DEG C, pressure
For 22.5 ~ 50Mpa；
When the temperature of supercriticality is 460 ~ 600 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carries out gas
It is separated by solid-liquid separation, heavy metallic oxide remains in high-temperature high-pressure reaction kettle bottom, the gas cooling of reaction product system, three oxidations two
Arsenic gas is transformed into solid arsenic trioxide and settles down, and gas further cools down, and the isolated liquid of liquid phase is the water of bromine
Solution and gas are nitrogen oxides；
Reaction product system when the temperature of supercriticality is 375 ~ 460 DEG C (being free of 460 DEG C), in high-temperature high-pressure reaction kettle
Being cooled to temperature is 60 ~ 100 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, and it is three oxidations two that gas-solid-liquid three phase separation, which obtains solid,
Arsenic, liquid is the nitrate solution of heavy metal and gas is volatilization bromine.
The carbon adsorbent is active carbon, carbon nanotube, coke, activated carbon fibre, carbon black, charcoal, charcoal, graphene
And/or silicon carbide；Metal oxide sorbents are silica, titanium dioxide, active aluminum oxide, zirconium oxide, micropore point
Son sieve and/or mesopore molecular sieve；Mineral adsorbent is clay mineral and/or natural zeolite；
It is additionally added dressing agent while metallic bond is added in the step (1), metallic bond is phase transfer catalyst, gold
Belong to the 2 ~ 15% of the quality for the adsorbent that bonding agent is arsenic pollution, dressing agent is methanol, ethyl alcohol and/or acetone, the flow of dressing agent
For 1.5 ~ 18mL/min；
The phase transfer catalyst is bromination quaternized ammonium, and bromination quaternized ammonium is 4 bromide, tetraethylammonium bromide, four
Propyl ammonium bromide, tetrabutylammonium bromide, four pentyl ammonium bromide, four hexyl ammonium bromides, four heptyl ammonium bromides, ammonium bromide and tetraoctyl ammonium bromide,
Four nonyl ammonium bromides or four decyl ammonium bromides；
The oxidant of the step (2) is hydrogen peroxide, oxygen or ozone；
The high-temperature high-pressure reaction kettle is batch reactor or continuous reaction kettle.
The dressing agent (methanol, ethyl alcohol and/or acetone) contained in extract in the step (1) is carrying out supercritical water
It can use volatilization recycling before reaction；
Reaction process of the invention are as follows:
2BrO2=Br2+2O2
N→NO→NO2→HNO3
Br2+H2O=HBrO+HBr
3As+5HNO3+2H2O=3H3AsO4+5NO
2HBrO=2HBr+O2
HNO3+2HBr=Br2+NO2+H2O
AsO4 3-→As2O7 4-→AsO3 -→As2O5→As2O3
Phase transfer catalyst promotes reactant to dissolve in two-phase, and supercritical carbon dioxide efficiently extracts.
Beneficial effects of the present invention:
(1), can be by supercritical carbon dioxide low-temperature extraction after arsenic and quaternary ammonium salt instead give birth to associated reaction in the present invention, mild parsing is inhaled
Arsenic and heavy metal ion in attached dose；
(2) increase dissolution can be improved in dressing agent of the invention, improves the extraction yield of arsenic and heavy metal ion, quickly realizes and inhale
Attached dose of parsing；
(3) oxidation of supercritical water of the present invention, supercritical water and oxidizing gas, which dissolve each other, quickly aoxidizes extract containing arsenic
Arsenic trioxide is obtained, the nitrogen in bonding agent is oxidized rear generation nitric acid soluble in water, after the bromine in quaternary ammonium salt is oxidized,
Due to the presence of water and nitric acid, it can react and release nitrogen oxides, nitrogen oxides can be recycled in the form of nitric acid again, remaining
Aqueous solution is containing bromine aqueous solution；
(4) the method for the present invention utilizes high-temperature supercritical water state, and arsenic trioxide volatilization, other heavy metals are in the form of the oxide
Deposition recycling, is conducive to the collection and purifying of arsenic trioxide；
(5) the method for the present invention simple process, operating procedure is few, reduces reagent consumption, avoids secondary pollution, simplify technique stream
Journey.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1: in the present embodiment in the adsorbent of arsenic pollution arsenic content be 75g/kg, adsorbent be clay mineral and
Active carbon, the content of heavy metal copper is 0.78 g/kg in the adsorbent of arsenic pollution and the content of heavy metal iron is 0.44g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (tetrabutylammonium bromide),
Dressing agent (ethyl alcohol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 15min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 65 DEG C, pressure 50MPa；Gold
Belong to the 15% of the adsorbent mass that bonding agent (tetrabutylammonium bromide) is arsenic pollution, the flow of dressing agent (ethyl alcohol) is 1.5mL/
min；
(2) the extraction product of step (1), water, excessive oxidant (oxygen) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
Reach water supercriticality, and react 3min and obtain reaction product system, wherein the temperature of supercriticality is 600 DEG C, pressure
For 23Mpa；The metal oxide of the rapid pressure release of high-temperature high-pressure reaction kettle, copper and iron remains in high-temperature high-pressure reaction kettle bottom, instead
The gas cooling of product system is answered, arsenic trioxide gas transition settles down at solid arsenic trioxide, and gas is further cold
It but is 55 DEG C to temperature, the isolated liquid of liquid phase is the aqueous solution of bromine and gas is nitrogen oxides；
The present embodiment high-temperature high-pressure reaction kettle is batch reactor；
The ethyl alcohol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.81g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal copper is 0.010 g/
Kg, the content of heavy metal iron are 0.013g/kg, and the adsorption capacity of reproducing adsorbent is the 98.5% of original adsorbent, the three of recycling
The purity for aoxidizing two arsenic is 99.6%, and the rate of recovery of arsenic is 98.7%, and the rate of recovery of heavy metal copper and iron is 97.9%.
Embodiment 2: in the present embodiment in the adsorbent of arsenic pollution arsenic content be 95g/kg, adsorbent be carbon nanotube and
Titanium dioxide, the content of iron is 1.1 g/kg in the adsorbent of arsenic pollution, and the content of lead is 0.77g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (4 bromide),
Dressing agent (methanol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 5min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 35 DEG C, pressure 30MPa；Gold
Belong to the 8% of the adsorbent mass that bonding agent (4 bromide) is arsenic pollution, the flow of dressing agent (methanol) is 7.5mL/min；
(2) the extraction product of step (1), water, excessive oxidant (ozone) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
Reach water supercriticality, and react 15min and obtain reaction product system, wherein the temperature of supercriticality is 500 DEG C, pressure
For 28Mpa；The metal oxide of the rapid pressure release of high-temperature high-pressure reaction kettle, iron and lead remains in high-temperature high-pressure reaction kettle bottom, instead
The gas cooling of product system is answered, arsenic trioxide gas transition settles down at solid arsenic trioxide, and gas is further cold
It but is 50 DEG C to temperature, the isolated liquid of liquid phase is the aqueous solution of bromine and gas is nitrogen oxides；
The present embodiment high-temperature high-pressure reaction kettle is batch reactor；
The methanol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.95g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal iron is 0.009 g/
Kg, the content of lead are 0.011g/kg, and the adsorption capacity of reproducing adsorbent is the 97.0% of original adsorbent, three oxidations two of recycling
The purity of arsenic is 98.8%, and the rate of recovery of arsenic is 98.5%, and the overall recovery of heavy metal iron and lead is 98.5%.
Embodiment 3: the content of arsenic is 115g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is active carbon fibre
Peacekeeping zirconium oxide, the content of heavy metal copper is 0.65 g/kg in the adsorbent of arsenic pollution, the content of iron is 0.89 g/kg, lead
Content is 0.43g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, adds metallic bond (4-propyl bromide) simultaneously
It is passed through carbon dioxide gas, heating is forced into the supercriticality of carbon dioxide, and the regeneration that contact extraction 30min is parsed is inhaled
Attached dose and extraction product, wherein the temperature of CO 2 supercritical state is 45 DEG C, pressure 15MPa；Metallic bond (tetrapropyl
Ammonium bromide) be arsenic pollution adsorbent mass 10%；
(2) the extraction product of step (1), water, excessive oxidant (hydrogen peroxide) are added in high-temperature high-pressure reaction kettle II and are mixed
Reaction system uniformly is obtained, in confined conditions, reactant is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
System reaches water supercriticality, and reacts 10min and obtain reaction product system, and wherein the temperature of supercriticality is 460 DEG C, pressure
Power is 33Mpa；The rapid pressure release of high-temperature high-pressure reaction kettle, the metal oxide of copper, iron and lead remain in high-temperature high-pressure reaction kettle bottom
Portion, the gas cooling of reaction product system, arsenic trioxide gas transition settle down at solid arsenic trioxide, and gas is into one
It is 48 DEG C that step, which is cooled to temperature, and the isolated liquid of liquid phase is the aqueous solution of bromine and gas is nitrogen oxides；
The present embodiment high-temperature high-pressure reaction kettle is continuous reaction kettle；
The content of arsenic is down to 1.02g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal copper is 0.009 g/
Kg, iron content be 0.008 g/kg, the content of lead is 0.004g/kg, the adsorption capacity of reproducing adsorbent is original adsorbent
98.8%, the purity of the arsenic trioxide of recycling is 99.1%, and the rate of recovery of arsenic is 98.9%, and heavy metal copper, iron and the total of lead return
Yield is 97.9%.
Embodiment 4: the content of arsenic is 87g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is charcoal and day
Right zeolite, the content of heavy metal lead is 1.5 g/kg in the adsorbent of arsenic pollution, the content of chromium is 0.64g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (tetraethylammonium bromide),
Dressing agent (ethyl alcohol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 90min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 55 DEG C, pressure 7.5MPa；Gold
Belong to the 15% of the adsorbent mass that bonding agent (tetraethylammonium bromide) is arsenic pollution, the flow of dressing agent (ethyl alcohol) is 18mL/min；
(2) the extraction product of step (1), water, excessive oxidant (ozone) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
Reach water supercriticality, and react 30min and obtain reaction product system, wherein the temperature of supercriticality is 550 DEG C, pressure
For 38Mpa；The metal oxide of the rapid pressure release of high-temperature high-pressure reaction kettle, lead and chromium remains in high-temperature high-pressure reaction kettle bottom, instead
The gas cooling of product system is answered, arsenic trioxide gas transition settles down at solid arsenic trioxide, and gas is further cold
It but is 50 DEG C to temperature, the isolated liquid of liquid phase is bromine aqueous solution and gas is nitrogen oxides；
The present embodiment high-temperature high-pressure reaction kettle is batch reactor；
The ethyl alcohol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 1.07g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal lead is in adsorbent
0.013 g/kg, chromium content be 0.009g/kg, the adsorption capacity of reproducing adsorbent is the 97.6% of original adsorbent, recycling
The purity of arsenic trioxide is 99.3%, and the rate of recovery of arsenic is 97.8%, and the overall recovery of heavy metal lead and chromium is 98.3%.
Embodiment 5: the content of arsenic is 90g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is micro porous molecular sieve
With active aluminum oxide, the content of heavy metal lead is 2.3 g/kg in the adsorbent of arsenic pollution, the content of cadmium is 1.8g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (four decyl ammonium bromides),
Dressing agent (methanol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 50min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 75 DEG C, pressure 45MPa；Gold
Belong to the 12% of the adsorbent mass that bonding agent (four decyl ammonium bromides) is arsenic pollution, the flow of dressing agent (methanol) is 15mL/min；
(2) the extraction product of step (1), water, oxidant (oxygen) are added in high-temperature high-pressure reaction kettle II and are uniformly mixed
To reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II and is reached
Water supercriticality, and react 25min and obtain reaction product system, wherein the temperature of supercriticality is 430 DEG C, and pressure is
45Mpa；It is 60 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, the rapid pressure release of high-temperature high-pressure reaction kettle,
It is arsenic trioxide that gas-solid-liquid three phase separation, which obtains solid, and liquid is the nitrate solution of lead and cadmium and gas is volatilization bromine；
The present embodiment high-temperature high-pressure reaction kettle is batch reactor；
The methanol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 1.21g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal lead is in adsorbent
0.0139g/kg, cadmium content be 0.019g/kg, the adsorption capacity of reproducing adsorbent is the 98.3% of original adsorbent, recycling
The purity of arsenic trioxide is 98.9%, and the rate of recovery of arsenic is 99.0%, and the overall recovery of heavy metal lead and cadmium is 98.8%.
Embodiment 6: the content of arsenic is 40g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is carbon black and dioxy
SiClx, the content of heavy metal cadmium is 1.91 g/kg in the adsorbent of arsenic pollution, the content of chromium is 1.75g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (ammonium bromide and tetraoctyl ammonium bromide),
Dressing agent (methanol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 80min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 85 DEG C, pressure 40MPa；Gold
Belong to the 5% of the adsorbent mass that bonding agent (ammonium bromide and tetraoctyl ammonium bromide) is arsenic pollution, the flow of dressing agent (methanol) is 13mL/min；
(2) the extraction product of step (1), water, excessive oxidant (oxygen) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
Reach water supercriticality, and react 35min and obtain reaction product system, wherein the temperature of supercriticality is 375 DEG C, pressure
For 48Mpa；It is 95 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, and high-temperature high-pressure reaction kettle is let out rapidly
Pressure, it is arsenic trioxide that gas-solid-liquid three phase separation, which obtains solid, and liquid is the nitrate solution of cadmium and chromium and gas is volatilization bromine；
The present embodiment high-temperature high-pressure reaction kettle is batch reactor；
The methanol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.067g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal cadmium is in adsorbent
0.012 g/kg, chromium content be 0.014g/kg, the adsorption capacity of reproducing adsorbent is the 98.5% of original adsorbent, recycling
The purity of arsenic trioxide is 99.3%, and the rate of recovery of arsenic is 97.6%, and the overall recovery of heavy metal cadmium and chromium is 97.8%.
Embodiment 7: the content of arsenic is 60g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is charcoal and coke
Charcoal, the content of heavy metal copper is 1.87 g/kg in the adsorbent of arsenic pollution, the content of chromium is 0.96g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (four heptyl ammonium bromides),
Dressing agent (acetone) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 70min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 70 DEG C, pressure 50MPa；Gold
Belong to the 8% of the adsorbent mass that bonding agent (four heptyl ammonium bromides) is arsenic pollution, the flow of dressing agent (acetone) is 6.5mL/min；
(2) the extraction product of step (1), water, excessive oxidant (hydrogen peroxide) are added in high-temperature high-pressure reaction kettle II and are mixed
Reaction system uniformly is obtained, in confined conditions, reactant is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
System reaches water supercriticality, and reacts 25min and obtain reaction product system, and wherein the temperature of supercriticality is 400 DEG C, pressure
Power is 50Mpa；It is 70 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, and high-temperature high-pressure reaction kettle is let out rapidly
Pressure, it is arsenic trioxide that gas-solid-liquid three phase separation, which obtains solid, and liquid is the nitrate solution of copper and chromium and gas is volatilization bromine；
The present embodiment high-temperature high-pressure reaction kettle is continuous reaction kettle；
The acetone contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.044g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal copper is in adsorbent
0.019 g/kg, chromium content be 0.010g/kg, the adsorption capacity of reproducing adsorbent is the 97.7% of original adsorbent, recycling
The purity of arsenic trioxide is 99.0%, and the rate of recovery of arsenic is 98.2%, and the overall recovery of heavy metal copper and chromium is 98.3%.
Embodiment 8: the content of arsenic is 78g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is graphene and carbon
SiClx, in the adsorbent of arsenic pollution the content of heavy metal iron be 1.76 g/kg, chromium content 2.14g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (four hexyl ammonium bromides),
Dressing agent (acetone) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 60min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 60 DEG C, pressure 25MPa；Gold
Belong to the 12% of the adsorbent mass that bonding agent (four hexyl ammonium bromides) is arsenic pollution, the flow of dressing agent (acetone) is 11mL/min；
(2) the extraction product of step (1), water, excessive oxidant (hydrogen peroxide) are added in high-temperature high-pressure reaction kettle II and are mixed
Reaction system uniformly is obtained, in confined conditions, reactant is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
System reaches water supercriticality, and reacts 15min and obtain reaction product system, and wherein the temperature of supercriticality is 425 DEG C, pressure
Power is 40Mpa；It is 80 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, and high-temperature high-pressure reaction kettle is let out rapidly
Pressure, it is arsenic trioxide that gas-solid-liquid three phase separation, which obtains solid, and liquid is the nitrate solution of iron and chromium and gas is volatilization bromine；
The present embodiment high-temperature high-pressure reaction kettle is continuous reaction kettle；
The acetone contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.089g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal iron is in adsorbent
0.011 g/kg, chromium content be 0.021g/kg, the adsorption capacity of reproducing adsorbent is the 98.5% of original adsorbent, recycling
The purity of arsenic trioxide is 99.5%, and the rate of recovery of arsenic is 98.2%, and the overall recovery of heavy metal iron and chromium is 98.3%.
Embodiment 9: the content of arsenic is 95g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is mesoporous molecular
It sieves, the content of heavy metal iron is 2.1 g/kg in the adsorbent of arsenic pollution, the content of chromium is 1.57 g/kg and cadmium content is
1.78g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (four pentyl ammonium bromide),
Dressing agent (ethyl alcohol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 40min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 50 DEG C, pressure 15MPa；Gold
Belong to the 2% of the adsorbent mass that bonding agent (four pentyl ammonium bromide) is arsenic pollution, the flow of dressing agent (ethyl alcohol) is 5mL/min；
(2) the extraction product of step (1), water, excessive oxidant (ozone) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II and reaches water supercritical state
State, and react 8min and obtain reaction product system, wherein the temperature of supercriticality is 450 DEG C, pressure 22.5Mpa；High temperature
It is 90 DEG C that reaction product system in autoclave, which is cooled to temperature, the rapid pressure release of high-temperature high-pressure reaction kettle, gas-solid-liquid three-phase
Isolated solid is arsenic trioxide, and liquid is the nitrate solution of iron, chromium and cadmium and gas is volatilization bromine；
The present embodiment high-temperature high-pressure reaction kettle is continuous reaction kettle；
The ethyl alcohol contained in extract in the present embodiment step (1) can use volatilization recycling before carrying out supercritical water reaction；
The content of arsenic is down to 0.088g/kg in the reproducing adsorbent of the present embodiment parsing, and the content of heavy metal iron is in adsorbent
0.017 g/kg, chromium content be 0.014g/kg and the content of cadmium is 0.009g/kg, the adsorption capacity of reproducing adsorbent is original
Have the 98.8% of adsorbent, the purity of the arsenic trioxide of recycling is 99.2%, and the rate of recovery of arsenic is 98.3%, heavy metal iron, chromium and
The overall recovery of cadmium is 98.2%.
Embodiment 10: the content of arsenic is 62g/kg in the adsorbent of arsenic pollution in the present embodiment, and adsorbent is active carbon fibre
It ties up, the content of heavy metal lead is 0.95g/kg in the adsorbent of arsenic pollution, the content of zinc is 0.87 g/kg, the content of copper is
1.43 g/kg and chromium content are 1.22g/kg；
A kind of method of the adsorbent reactivation of arsenic pollution and arsenic recycling, specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, add metallic bond (tetrabutylammonium bromide),
Dressing agent (ethyl alcohol) is simultaneously passed through carbon dioxide gas, and heating is forced into the supercriticality of carbon dioxide, and contact extraction 30min is obtained
To the reproducing adsorbent and extraction product of parsing, wherein the temperature of CO 2 supercritical state is 45 DEG C, pressure 10MPa；Gold
Belong to the 15% of the adsorbent mass that bonding agent (tetrabutylammonium bromide) is arsenic pollution, the flow of dressing agent (ethyl alcohol) is 8mL/min；
(2) the extraction product of step (1), water, excessive oxidant (oxygen) are added in high-temperature high-pressure reaction kettle II and are mixed
It is even to obtain reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle II
Reach water supercriticality, and react 20min and obtain reaction product system, wherein the temperature of supercriticality is 575 DEG C, pressure
For 27.5Mpa；The rapid pressure release of high-temperature high-pressure reaction kettle, lead, zinc, copper and chromium metal oxide remain in high-temperature high-pressure reaction kettle
Bottom, the gas cooling of reaction product system, arsenic trioxide gas transition settle down at solid arsenic trioxide, gas into
It is 45 DEG C that one step, which is cooled to temperature, and the isolated liquid of liquid phase is the aqueous solution of bromine and gas is nitrogen oxides；
The present embodiment high-temperature high-pressure reaction kettle is continuous reaction kettle；
The content of arsenic is down to 0.075g/kg in the reproducing adsorbent of the present embodiment parsing, heavy metal lead in adsorbent, zinc, copper and
Chromium content is respectively 0.009,0.015,0.012 and 0.08g/kg, and the adsorption capacity of reproducing adsorbent is original adsorbent
98.8%, the purity of the arsenic trioxide of recycling is 99.5%, and the rate of recovery of arsenic is 98.7%, heavy metal lead, zinc, copper and chromium it is total
The rate of recovery is 97.8%.
Claims (6)
1. a kind of method of adsorbent reactivation of arsenic pollution and arsenic recycling, which is characterized in that specific steps are as follows:
(1) adsorbent of arsenic pollution is placed in high-temperature high-pressure reaction kettle I, adds metallic bond and is passed through carbon dioxide gas
Body, heating are forced into the supercriticality of carbon dioxide, the reproducing adsorbent and extraction that 5 ~ 90min of contact extraction is parsed
Product, wherein the temperature of CO 2 supercritical state is 35 ~ 85 DEG C, and pressure is 7.5 ~ 50Mpa；Adsorbent is carbon adsorbent, gold
Belong to oxide adsorbent and/or mineral adsorbent；Heavy metal ion containing pollution adsorbent in the adsorbent of arsenic pollution；
(2) extraction product, water, the excessive oxidant of step (1) are added to be uniformly mixed in high-temperature high-pressure reaction kettle II and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle II and reaches water in confined conditions
Supercriticality, and react 3 ~ 35 min and obtain reaction product system, wherein the temperature of supercriticality is 375 ~ 600 DEG C, pressure
Power is 22.5 ~ 50Mpa；
When the temperature of supercriticality is 460 ~ 600 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carries out gas
It is separated by solid-liquid separation, heavy metallic oxide remains in high-temperature high-pressure reaction kettle bottom；The gas cooling of reaction product system, three oxidations two
Arsenic gas is transformed into solid arsenic trioxide and settles down, and gas further cools down, and the isolated liquid of liquid phase is the water of bromine
Solution and gas are nitrogen oxides；
Reaction product system when the temperature of supercriticality is 375 ~ 460 DEG C (being free of 460 DEG C), in high-temperature high-pressure reaction kettle
Being cooled to temperature is 60 ~ 100 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, and it is three oxidations two that gas-solid-liquid three phase separation, which obtains solid,
Arsenic, liquid is the nitrate solution of heavy metal and gas is volatilization bromine.
2. the method for adsorbent reactivation Yu the arsenic recycling of arsenic pollution according to claim 1, it is characterised in that: carbon adsorbent is
Active carbon, carbon nanotube, coke, activated carbon fibre, carbon black, charcoal, charcoal, graphene and/or silicon carbide；Metal oxide
Adsorbent is silica, titanium dioxide, active aluminum oxide, zirconium oxide, micro porous molecular sieve and/or mesopore molecular sieve；Mine
Object adsorbent is clay mineral and/or natural zeolite.
3. the method for adsorbent reactivation Yu the arsenic recycling of arsenic pollution according to claim 1, it is characterised in that: in step (1)
It is additionally added dressing agent while metallic bond is added, metallic bond is phase transfer catalyst, and metallic bond is arsenic pollution
Adsorbent quality 2 ~ 15%, dressing agent is methanol, ethyl alcohol and/or acetone, and the flow of dressing agent is 1.5 ~ 18mL/min.
4. the method for adsorbent reactivation Yu the arsenic recycling of arsenic pollution according to claim 3, it is characterised in that: phase transfer catalysis (PTC)
Agent is bromination quaternized ammonium, and bromination quaternized ammonium is 4 bromide, tetraethylammonium bromide, 4-propyl bromide, the tetrabutyl
Ammonium bromide, four pentyl ammonium bromide, four hexyl ammonium bromides, four heptyl ammonium bromides, ammonium bromide and tetraoctyl ammonium bromide, four nonyl ammonium bromides or four last of the ten Heavenly stems
Base ammonium bromide.
5. the method for adsorbent reactivation Yu the arsenic recycling of arsenic pollution according to claim 1, it is characterised in that: step (2)
Oxidant is hydrogen peroxide, oxygen or ozone.
6. the method for adsorbent reactivation Yu the arsenic recycling of arsenic pollution according to claim 1, it is characterised in that: high temperature high pressure reverse
Answering kettle is batch reactor or continuous reaction kettle.
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| CN112374473A (en) * | 2020-11-11 | 2021-02-19 | 深圳大学 | Phenol organic matter doped g-C synthesized based on phenol-containing wastewater3N4Method (2) |
| CN114588876A (en) * | 2022-01-18 | 2022-06-07 | 中国科学院武汉岩土力学研究所 | Arsenic adsorption material and preparation and recycling method thereof |
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