CN109179621A - A kind of supercritical water treatment method of arsenic-containing waste water - Google Patents
A kind of supercritical water treatment method of arsenic-containing waste water Download PDFInfo
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- CN109179621A CN109179621A CN201810859896.7A CN201810859896A CN109179621A CN 109179621 A CN109179621 A CN 109179621A CN 201810859896 A CN201810859896 A CN 201810859896A CN 109179621 A CN109179621 A CN 109179621A
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- arsenic
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 124
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000002351 wastewater Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 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 41
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 40
- 239000000047 product Substances 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 23
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002912 waste gas Substances 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 9
- 150000004706 metal oxides Chemical group 0.000 abstract description 8
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 235000010269 sulphur dioxide Nutrition 0.000 description 9
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- -1 organic flocculant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency 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
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
-
- 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
Abstract
The present invention relates to a kind of supercritical water treatment methods of arsenic-containing waste water, belong to field of waste water treatment.Oxidant, arsenic-containing waste water, additive are added in high-temperature high-pressure reaction kettle and obtain reaction system by the present invention, in confined conditions, are forced into reaction system to reaction system heating and reach supercriticality, 8 ~ 115min of reaction obtains reaction product system；When the temperature of supercriticality is 460 ~ 630 DEG C, rapid pressure release, the separation of reaction product system gas-solid-liquid, solid product is metal oxide in autoclave body, gaseous product is cooling, and arsenic trioxide is settled down by gas transition at solid, and product liquid is the solution of nitric acid；When the temperature of supercriticality is 385 ~ 460 DEG C (being free of 460 DEG C), it is 100 DEG C or less that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, form waste gas of sulfur dioxide is passed through to react to obtain solid product and product liquid, separation of solid and liquid obtains solid arsenic trioxide and product liquid, and wherein product liquid is the mixed acid solution containing metal cation.
Description
Technical field
The present invention relates to a kind of supercritical water treatment methods of arsenic-containing waste water, belong to field of waste water treatment.
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.In recent years, the extensive use with a large amount of exploitations of metallic ore and arsenic industrially, arsenic-containing waste water, waste residue amount increasingly increase
Add, arsenic environmental pollution is on the rise.Therefore, the innoxious and recycling treatment of arsenic-containing waste water is necessary.Processing is useless containing arsenic
Water main method has extraction, vulcanization, embrane method, ion-exchange, absorption method, in the lime and side such as molysite coagulant sedimentation
Method.
A kind of method that arsenic-containing waste water precipitating is converted into arsenic trioxide, benefit are disclosed in Chinese patent CN102718259B
With alkali neutralization, copper sulfate precipitate, alkali is adjusted, and adds sulfuric acid dissolution, is passed through sulphur dioxide reduction, then pass through and heat, is cooling, crystallizing,
Arsenic trioxide is obtained by filtration, consumes a large amount of acid-base reagents.A kind of low concentration is disclosed in Chinese patent CN102234160B
Method for treating arsenic-containing wastewater adjusts pH using the plaster of paris (milk of lime), oxidizing, sequentially adds inorganic coagulant, a huge sum of money
Belong to agent for capturing, caustic soda, organic flocculant, surfactant, flotation, the filtering of clear liquid film is recycled to have reached standard, it could not be effective
Recycling arsenic resource.A kind of processing method of arsenic-containing waste water is disclosed in Chinese patent CN103112974B, by acid for adjusting pH,
Multistage launches sulfide, and precipitation and separation adds alkali to adjust, electrolysis-coagulation, electrofloatation, electrolysis oxidation-reduction, aeration and sedimentation, finally
By being separated by solid-liquid separation, but technical solution of the present invention is complicated and the device that is related to is more, and input cost is big.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of supercritical water treatment method of arsenic-containing waste water, sides of the present invention
Method simple process, operating procedure is few, reduces reagent consumption, avoids secondary pollution, simplify process flow.
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant, arsenic-containing waste water, nitrogenous additive are added in high-temperature high-pressure reaction kettle and obtain reaction system, closed
Under the conditions of, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches supercriticality, and react 8 ~
115min obtains reaction product system, and wherein the temperature of supercriticality is 385 ~ 630 DEG C, and pressure is 24 ~ 54Mpa；
When the temperature of supercriticality is 460 ~ 630 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carries out gas
Be separated by solid-liquid separation, residual high temperature and pressure autoclave body bottom solid product be heavy metallic oxide, the gas cooling of reaction product system,
Arsenic trioxide gas transition settles down at solid arsenic trioxide, and further cooling, product liquid is nitric acid solution；
Reaction product system when the temperature of supercriticality is 385 ~ 460 DEG C (being free of 460 DEG C), in high-temperature high-pressure reaction kettle
It is cooled to temperature to react to obtain solid product and product liquid hereinafter, being passed through form waste gas of sulfur dioxide for 100 DEG C, separation of solid and liquid obtains
Solid arsenic trioxide and product liquid, product liquid are the mixed acid solution containing metal cation, and wherein mixed acid is nitre
The mixed acid of acid and sulfuric acid.
The oxidant is hydrogen peroxide, oxygen or ozone.
The nitrogenous additive is ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium acetate, ammonium hydroxide, nitric oxide, nitrogen dioxide
One or more, the molar ratio of the arsenic atom in the nitrogen-atoms and arsenic sulfide slag in nitrogenous additive is (3 ~ 11): 1.
Further, the high-temperature high-pressure reaction kettle is batch reactor or continuous reaction kettle；
Further, the arsenic-containing waste water is inorganic arsenic waste water and/or organo-arsenic waste water；
Further, the nitric acid solution of the generation may be reused.
Beneficial effects of the present invention:
(1) water in the present invention under supercriticality dissolves each other with oxidizing gas, and be divided by interphase mass transfer resistance, can quick oxygen
Change arsenic-containing waste water (including debirs), accelerates delivery rate, increase operation rate；
(2) under supercriticality of the present invention, nitrogenous additive is oxidized output nitric acid, further aoxidizes organo-arsenic and inorganic arsenic,
Arsenic can be made to exist in the form of arsenic acid；
(3) oxidation of supercritical water of the present invention, in the presence of nitric acid, in supercritical water vaporization at high temperature stage (temperature 460
~ 600 DEG C), using other metals in the i.e. separable waste water of high temperature pressure release mode, in a kettle with oxide (nitrate
Decompose and oxidant oxidation) form exist；In the supercritical water sub-cooled stage, other metals are in waste water with ion
Form is present in the mixed acid solution of nitric acid and sulfuric acid；
(4) the method for the present invention utilizes high-temperature supercritical water state, arsenic trioxide volatilization, other metals sink in the form of the oxide
Product, is conducive to the collection and purifying of arsenic trioxide；Arsenic trioxide is precipitated in sub-cooled process, sulphur dioxide reduction arsenic acid,
Sulfur dioxide is oxidized to sulfur trioxide generation sulfuric acid soluble in water, and other metals are molten since the acidity of nitric acid and sulfuric acid acts on
Solution is in the mixed acid solution of nitric acid and sulfuric acid；
(5) directly arsenic trioxide is precipitated using form waste gas of sulfur dioxide reduction in the present invention, comprehensively utilizes exhaust gas, reduces pollution；(6)
The method of the present invention, can be with advanced treating arsenic-containing waste water, and simple process, operating procedure is few, simplifies process flow.
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: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 3.89g/L, dioxy
The mass concentration for changing sulphur SO 2 in waste gas is 9.5g/m3；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (oxygen), arsenic-containing waste water, nitrogenous additive (ammonium hydroxide) are added in high-temperature high-pressure reaction kettle and obtained instead
System is answered, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches overcritical
State, and react 8min and obtain reaction product system, wherein the temperature of supercriticality is 430 DEG C, pressure 40Mpa；High temperature
It is 95 DEG C that reaction product system in autoclave, which is cooled to temperature, be passed through form waste gas of sulfur dioxide react to obtain solid product and
Product liquid, separation of solid and liquid obtain solid arsenic trioxide and product liquid, and product liquid is the mixing containing metal cation
Acid solution, wherein mixed acid is the mixed acid of nitric acid and sulfuric acid；Nitrogen-atoms and arsenic atom in arsenones in nitrogenous additive ammonium hydroxide
Molar ratio be 6:1；
The present embodiment high temperature autoclave is batch reactor；
The content that the present embodiment contains arsenic in the mixed acid solution of metal cation is 0.35mg/L, is lower than national emission standard
0.5mg/L, the purity of arsenic trioxide are 99.6%, and the rate of recovery of arsenic is 98.2%.
Embodiment 2: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 5.41g/L；Dioxy
The mass concentration for changing sulphur SO 2 in waste gas is 7.5g/m3；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (oxygen), arsenic-containing waste water, nitrogenous additive (ammonium sulfate) are added in high-temperature high-pressure reaction kettle and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle and reaches super and face in confined conditions
Boundary's state, and react 115min and obtain reaction product system, wherein the temperature of supercriticality is 385 DEG C, pressure 30Mpa；
It is 90 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, is passed through form waste gas of sulfur dioxide and reacts to obtain solid production
Object and product liquid, separation of solid and liquid obtain solid arsenic trioxide and product liquid, and product liquid is to contain metal cation
Mixed acid solution, wherein mixed acid is the mixed acid of nitric acid and sulfuric acid；In nitrogenous additive ammonium sulfate in nitrogen-atoms and arsenones
The molar ratio of arsenic atom is 11:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
The content of arsenic is 0.43mg/L in mixed acid solution in the present embodiment containing metal cation, is lower than national emission standard
0.5mg/L, the purity of arsenic trioxide are 99.3%, and the rate of recovery of arsenic is 97.8%.
Embodiment 3: arsenic-containing waste water is waste water containing organo-arsenic in the present embodiment, and the content of arsenic in waste water is 4.56g/L；Dioxy
The mass concentration for changing sulphur SO 2 in waste gas is 8g/m3；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (ammonium acetate) are added in high-temperature high-pressure reaction kettle and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle and reaches super and face in confined conditions
Boundary's state, and react 55min and obtain reaction product system, wherein the temperature of supercriticality is 400 DEG C, pressure 24Mpa；It is high
It is 85 DEG C that reaction product system in warm autoclave, which is cooled to temperature, is passed through form waste gas of sulfur dioxide and reacts to obtain solid product
And product liquid, separation of solid and liquid obtain solid arsenic trioxide and product liquid, product liquid is mixed containing metal cation
Acid solution is closed, wherein mixed acid is the mixed acid of nitric acid and sulfuric acid；Nitrogen-atoms and arsenic in arsenones in nitrogenous additive ammonium acetate
The molar ratio of atom is 7:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
The content of arsenic is 0.45mg/L in mixed acid solution in the present embodiment containing metal cation, is lower than national emission standard
0.5mg/L, the purity of arsenic trioxide are 99.4%, and the rate of recovery of arsenic is 98.2%.
Embodiment 4: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 5.34g/L；Dioxy
The mass concentration for changing sulphur SO 2 in waste gas is 10g/m3；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (hydrogen peroxide), arsenic-containing waste water, nitrogenous additive (ammonium carbonate) are added in high-temperature high-pressure reaction kettle and obtained
To reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches super
Critical state, and react 75min and obtain reaction product system, wherein the temperature of supercriticality is 455 DEG C, pressure 44Mpa；
It is 90 DEG C that reaction product system in high-temperature high-pressure reaction kettle, which is cooled to temperature, is passed through form waste gas of sulfur dioxide and reacts to obtain solid production
Object and product liquid, separation of solid and liquid obtain solid arsenic trioxide and product liquid, and product liquid is to contain metal cation
Mixed acid solution, wherein mixed acid is the mixed acid of nitric acid and sulfuric acid；In nitrogenous additive ammonium carbonate in nitrogen-atoms and arsenones
The molar ratio of arsenic atom is 9:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
The content of arsenic is 0.45mg/L in mixed acid solution in the present embodiment containing metal cation, is lower than national emission standard
0.5mg/L, the purity of arsenic trioxide are 99.3%, and the rate of recovery of arsenic is 96.5%.
Embodiment 5: arsenic-containing waste water is waste water containing organo-arsenic in the present embodiment, and the content of arsenic in waste water is 7.62g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (ammonium acetate) are added in high-temperature high-pressure reaction kettle and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle and reaches super and face in confined conditions
Boundary's state, and react 35min and obtain reaction product system, wherein the temperature of supercriticality is 460 DEG C, pressure 54Mpa；It is high
The warm rapid pressure release of autoclave, reaction product system carry out gas-solid-liquid separation, and the solid of residual high temperature and pressure autoclave body bottom produces
Object is heavy metallic oxide, the gas cooling of reaction product system, and arsenic trioxide gas transition is heavy at solid arsenic trioxide
It lowers, further cooling, product liquid is the solution of nitric acid；Nitrogen-atoms and arsenic in arsenones are former in nitrogenous additive ammonium acetate
The molar ratio of son is 5:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.39mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.7%, and the rate of recovery of arsenic is 97.4%.
Embodiment 6: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 6.12g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (ammonium nitrate) are added in high-temperature high-pressure reaction kettle and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle and reaches super and face in confined conditions
Boundary's state, and react 95min and obtain reaction product system, wherein the temperature of supercriticality is 485 DEG C, pressure 34Mpa；It is high
The warm rapid pressure release of autoclave, reaction product system carry out gas-solid-liquid separation, and the solid of residual high temperature and pressure autoclave body bottom produces
Object is heavy metallic oxide, the gas cooling of reaction product system, and arsenic trioxide gas transition is heavy at solid arsenic trioxide
It lowers, further cooling, product liquid is the solution of nitric acid；Nitrogen-atoms and arsenic in arsenones are former in nitrogenous additive ammonium nitrate
The molar ratio of son is 10:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.46mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.5%, and the rate of recovery of arsenic is 98.3%.
Embodiment 7: arsenic-containing waste water is waste water containing organo-arsenic in the present embodiment, and the content of arsenic in waste water is 5.86g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (oxygen), arsenic-containing waste water, nitrogenous additive (nitrogen dioxide) are added in high-temperature high-pressure reaction kettle and obtained
To reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches super
Critical state, and react 32min and obtain reaction product system, wherein the temperature of supercriticality is 630 DEG C, pressure 40Mpa；
The rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carry out gas-solid-liquid separation, remain the solid of high temperature and pressure autoclave body bottom
Product is heavy metallic oxide, and the gas cooling of reaction product system, arsenic trioxide gas transition is at solid arsenic trioxide
It settles down, further cooling, product liquid is the solution of nitric acid；In nitrogenous additive nitrogen dioxide in nitrogen-atoms and arsenones
The molar ratio of arsenic atom is 9.5:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.37mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.3%, and the rate of recovery of arsenic is 97.7%.
Embodiment 8: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 5.76g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (hydrogen peroxide), arsenic-containing waste water, nitrogenous additive (nitric oxide) are added in high-temperature high-pressure reaction kettle
Reaction system is obtained, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and is reached
Supercriticality, and react 65min and obtain reaction product system, wherein the temperature of supercriticality is 590 DEG C, and pressure is
30Mpa；The rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carry out gas-solid-liquid separation, remain high temperature and pressure autoclave body bottom
Solid product be heavy metallic oxide, the gas cooling of reaction product system, arsenic trioxide gas transition is at three oxygen of solid
Change two arsenic to settle down, further cooling, product liquid is the solution of nitric acid；Nitrogen-atoms and sulphur in nitrogenous additive nitric oxide
The molar ratio for changing arsenic atom in arsenic is 4:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.41mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.5%, and the rate of recovery of arsenic is 96.3%.
Embodiment 9: arsenic-containing waste water is waste water containing organo-arsenic in the present embodiment, and the content of arsenic in waste water is 6.42g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (ammonium hydroxide) are added in high-temperature high-pressure reaction kettle and obtained instead
System is answered, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches overcritical
State, and react 40min and obtain reaction product system, wherein the temperature of supercriticality is 550 DEG C, pressure 28Mpa；High temperature
The rapid pressure release of autoclave, reaction product system carry out gas-solid-liquid separation, remain the solid product of high temperature and pressure autoclave body bottom
For heavy metallic oxide, the gas cooling of reaction product system, arsenic trioxide gas transition is settled at solid arsenic trioxide
Get off, further cooling, product liquid is the solution of nitric acid；Nitrogen-atoms and arsenic atom in arsenones in nitrogenous additive ammonium hydroxide
Molar ratio is 8:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.22mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.1%, and the rate of recovery of arsenic is 98.2%.
Embodiment 10: arsenic-containing waste water is waste water containing inorganic arsenic in the present embodiment, and the content of arsenic in waste water is 5.32g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (nitric oxide) are added in high-temperature high-pressure reaction kettle and obtained
To reaction system, in confined conditions, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches super
Critical state, and react 55min and obtain reaction product system, wherein the temperature of supercriticality is 575 DEG C, pressure 50Mpa；
The rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carry out gas-solid-liquid separation, remain the solid of high temperature and pressure autoclave body bottom
Product is heavy metallic oxide, and the gas cooling of reaction product system, arsenic trioxide gas transition is at solid arsenic trioxide
It settles down, further cooling, product liquid is the solution of nitric acid；In nitrogenous additive nitric oxide in nitrogen-atoms and arsenones
The molar ratio of arsenic atom is 6:1；
The present embodiment high temperature autoclave is continuous reaction kettle；
The present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.27mg/L, lower than country
Discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.3%, and the rate of recovery of arsenic is 97.5%.
Embodiment 11: arsenic-containing waste water is waste water containing organo-arsenic in the present embodiment, and the content of arsenic in waste water is 3.88g/L；
A kind of supercritical water treatment method of arsenic-containing waste water, specific steps are as follows:
Excessive oxidant (ozone), arsenic-containing waste water, nitrogenous additive (ammonium nitrate) are added in high-temperature high-pressure reaction kettle and are obtained
Reaction system is forced into reaction system to the reaction system heating in high-temperature high-pressure reaction kettle and reaches super and face in confined conditions
Boundary's state, and react 18min and obtain reaction product system, wherein the temperature of supercriticality is 525 DEG C, pressure 48Mpa；It is high
The warm rapid pressure release of autoclave, reaction product system carry out gas-solid-liquid separation, and the solid of residual high temperature and pressure autoclave body bottom produces
Object is heavy metallic oxide, the gas cooling of reaction product system, and arsenic trioxide gas transition is heavy at solid arsenic trioxide
It lowers, further cooling, product liquid is the solution of nitric acid；Nitrogen-atoms and arsenic in arsenones are former in nitrogenous additive ammonium nitrate
The molar ratio of son is 3:1；
The present embodiment high temperature autoclave is batch reactor；
In the present embodiment, using metal oxide in nitric acid-sulfuric acid method resolution autoclave body, the content of arsenic is 0.30mg/L, is lower than state
Family discharge standard 0.5mg/L, the purity of arsenic trioxide are 99.7%, and the rate of recovery of arsenic is 98.4%.
Claims (4)
1. a kind of supercritical water treatment method of arsenic-containing waste water, which is characterized in that specific steps are as follows:
Excessive oxidant, arsenic-containing waste water, nitrogenous additive are added in high-temperature high-pressure reaction kettle and obtain reaction system, closed
Under the conditions of, reaction system is forced into the reaction system heating in high-temperature high-pressure reaction kettle and reaches supercriticality, and react 8 ~
115min obtains reaction product system, and wherein the temperature of supercriticality is 385 ~ 630 DEG C, and pressure is 24 ~ 54Mpa；
When the temperature of supercriticality is 460 ~ 630 DEG C, the rapid pressure release of high-temperature high-pressure reaction kettle, reaction product system carries out gas
Gu separation, residual high temperature and pressure autoclave body bottom solid product be heavy metallic oxide, the gas cooling of reaction product system, three
It aoxidizes two arsenic gas and is transformed into solid arsenic trioxide and settle down, further cooling, product liquid is the solution of nitric acid；
Reaction product system when the temperature of supercriticality is 385 ~ 460 DEG C (being free of 460 DEG C), in high-temperature high-pressure reaction kettle
It is cooled to temperature to react to obtain solid product and product liquid hereinafter, being passed through form waste gas of sulfur dioxide for 100 DEG C, separation of solid and liquid obtains
Solid arsenic trioxide and product liquid, product liquid are the mixed acid solution containing metal cation, and wherein mixed acid is nitre
The mixed acid of acid and sulfuric acid.
2. the supercritical water treatment method of arsenic-containing waste water according to claim 1, it is characterised in that: oxidant be hydrogen peroxide,
Oxygen or ozone.
3. the supercritical water treatment method of arsenic sulfide slag according to claim 1, it is characterised in that: nitrogenous additive is sulfuric acid
One or more, the nitrogen original in nitrogenous additive of ammonium, ammonium nitrate, ammonium carbonate, ammonium acetate, ammonium hydroxide, nitric oxide, nitrogen dioxide
The molar ratio of son and the arsenic atom in arsenic sulfide slag is (3 ~ 11): 1.
4. the supercritical water treatment method of arsenic-containing waste water according to claim 1, it is characterised in that: high-temperature high-pressure reaction kettle is
Batch reactor or continuous reaction kettle.
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| CN112320771A (en) * | 2020-11-11 | 2021-02-05 | 深圳大学 | Thin-layer porous g-C prepared by supercritical water3N4Method (2) |
| CN115555387A (en) * | 2022-09-12 | 2023-01-03 | 昆明理工大学 | Method for degrading plastics in waste water and sludge |
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