CN107469767A - Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater and its application - Google Patents
Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater and its application Download PDFInfo
- Publication number
- CN107469767A CN107469767A CN201710827230.9A CN201710827230A CN107469767A CN 107469767 A CN107469767 A CN 107469767A CN 201710827230 A CN201710827230 A CN 201710827230A CN 107469767 A CN107469767 A CN 107469767A
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- Prior art keywords
- silica
- silicone zeolite
- titanium oxide
- cyanide
- nano titanium
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 156
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 131
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000010457 zeolite Substances 0.000 title claims abstract description 131
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 66
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000000741 silica gel Substances 0.000 claims abstract description 19
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- 239000000499 gel Substances 0.000 claims abstract description 13
- 238000007654 immersion Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000003750 conditioning effect Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 206010019909 Hernia Diseases 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 46
- 239000010949 copper Substances 0.000 abstract description 17
- 239000011701 zinc Substances 0.000 abstract description 16
- 229910052802 copper Inorganic materials 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 229910052725 zinc Inorganic materials 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 25
- 150000003376 silicon Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- -1 sulphur cyanogen Compound Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to technical field of waste water processing, and in particular to a kind of silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater and its application.Silica/nano titanium oxide/silicone zeolite the composite, its preparation method comprise the following steps：First silicone zeolite is mixed with sodium hydroxide solution, adding hole structure regulator, synthesize silicone zeolite gel, reacted, filtered, washed, dried, roasting, obtain silicone zeolite carrier；Silicone zeolite carrier, titanium dioxide nanoparticle are well mixed again, are pressed into thin slice, is calcined, silica gel immersion, drying, obtains silica/nano titanium oxide/silicone zeolite composite.Free Cyanide and complex cyanide are decomposed under the catalytic action of nano titanium oxide in the present invention, become nontoxic material, and zinc, copper heavy metal are then adsorbed to material surface, realize effective degraded to cyanogen in cyanide wastewater and effective absorption of heavy metal ion.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of silica/nanometer two of Treatment of Cyanide-containing Wastewater
Titanium oxide/silicone zeolite composite and its application.
Background technology
Cyanide wastewater is the larger waste water of plating production Poisoning.Because cyanide ion has good complexing, surface
Activity, activity function, cyaniding and leaching process of electroplating industry and gold industry etc. be a large amount of to use cyanide, and cyanide, sulphur cyanogen
Compound is extremely toxic material, therefore the improvement of cyanide wastewater is particularly important.
Cyanide ion and the cyanide ion with the complexing such as copper, zinc are usually contained in cyanide wastewater.At present, processing contains cyanogen
The method of waste water is a lot, and acidization is the technology that factory generally uses, and it can recovery of cyanide, but this method requirement to greatest extent
Closed system, the danger of hydrogen cyanide spilling be present, run complex operation, and the raffinate containing cyanogen after disposable processing does not reach country
Discharge standard, the difficulty in economic and technical is added to after-treatment.Copper-contained sludge caused by acidifying is difficult separation in addition, should
Technology one-time investment is excessive, and medium-sized and small enterprises are difficult to bear.
In addition, the method for Treatment of Cyanide-containing Wastewater also has the method for purification and the major class of method of reproduction two.The method of purification is using relevant
Chemicals destroy cyanide wastewater in cyanogen root complex ion, reduce cyanogen content；Method of reproduction be by cyanide recycling and
Valuable metal recovery.But due to the problems such as chlorine consumption is big, corrosivity is strong, cost is high, the method for purification and method of reproduction do not obtain industry
Change application.
Chinese patent CN105854790A discloses a kind of diatomite/composite titania material improvement gold industry and given up containing cyanogen
The method of water, this method comprise the following steps：Butyl titanate is mixed with absolute ethyl alcohol, is stirring evenly and then adding into deionized water,
Continue stirring to formation light yellow clear colloidal sol；Diatomite is added in light yellow clear colloidal sol, stirred, is stood, dry
To xerogel；Diatomite/composite titania material is obtained after xerogel is calcined；To diatomite/composite titania material
Middle addition cyanide wastewater, first vibrates, then carries out high voltage mercury lamp radiation；Obtain filter cake and filtrate after filtering, analyze in filtrate cyanogen and
The concentration of copper is simultaneously washed to filter cake.The patent, which is only referred to diatomite/composite titania material, with absorbing copper and to decompose
Cyanogen, but it is not directed to the absorption to zinc.
Chinese patent CN105749857A disclose it is a kind of administer high zinc, copper cyanide wastewater bentonite composite material and its should
With the preparation method of the patent is as follows：Butyl titanate, absolute ethyl alcohol and concentrated nitric acid are mixed to get mixture A；By six water nitric acid
Lanthanum is dissolved in deionized water, is added concentrated nitric acid, is added absolute ethyl alcohol and obtain mixture B；Mixture B is added drop-wise to mixture
In A, mixture C is obtained；After being added dropwise to complete, continue stirring and obtain milky white liquid；Add bentonite thereto, deionized water,
Obtain mixture D；Through precipitation, it is evaporated, grinds, sieve, roasting, is cooled to room temperature, obtains bentonite composite material.In the patent
The adsorbance of copper is 12.11-15.64mg/g, and the decomposition amount of cyanogen is 22.36-36.4mg/g, and the adsorbance of zinc is 18.11-
29.51mg/g, the adsorption capacity of degraded and heavy metal of the bentonite composite material to cyanogen are poor.
Chinese patent CN106693955A disclose a kind of bimetallic monoblock type plasma catalyst and preparation method thereof with
Using the patent uses excessive preparation catalyst, comprises the following steps that：Carrier is pre-processed, drying roasting；Make
By the use of water as solvent, γ-Al are added2O3Powder and active component, ultrasonic agitation；Pretreated cordierite honeycomb ceramic is put
Enter ultrasound in slurries, drying roasting obtains bimetallic monoblock type plasma catalyst.The patent is first by cordierite honeycomb ceramic
It is put in silica gel solution and impregnates as carrier, then will be by transition metal precursor salt, rare earth precursor salt, γ-Al2O3Powder
Presoma slurries prepared by end prepare bimetallic monoblock type plasma-catalytic with pretreated cordierite honeycomb ceramic carrier
Agent.The patent is soaked in the preparation process of carrier using silica gel, drying, 180 DEG C of roasting 1h, 400-600 DEG C of roasting
After 3h, then being loaded with active component presoma so that the silica gel being immersed on carrier causes damage, and before active component
Body is driven only by silica gel with carrier to be connected.
At present, when administering cyanide wastewater, its composite typically uses diatomite composite material or bentonite composite wood
Material, and these composites are relatively weak to the adsorption capacity of copper, zinc and cyanogen.
The content of the invention
It is an object of the invention to provide a kind of silica/nano titanium oxide/silicone zeolite of Treatment of Cyanide-containing Wastewater is compound
Material, realize effective degraded to cyanogen in cyanide wastewater and effective absorption of heavy metal ion；Should present invention simultaneously provides it
With.
Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater of the present invention, it is prepared
Method comprises the following steps：
(1) preparation of silicone zeolite carrier
Silicone zeolite is mixed with sodium hydroxide solution, adding hole structure regulator, synthesize silicone zeolite gel, reacted, filtering,
Washing, dry, roasting, obtain silicone zeolite carrier；
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Silicone zeolite carrier, titanium dioxide nanoparticle are well mixed, are pressed into thin slice, is calcined, silica gel immersion, drying, is obtained
To silica/nano titanium oxide/silicone zeolite composite.
Wherein：
In step (1), the mass ratio of silicone zeolite and sodium hydroxide solution is 1:2-9；
In step (1), the adding hole structure regulator under conditions of stirring, described whipping temp is 50-200 DEG C, stirred
It is 12-36 hours to mix the time；
In step (1), described pore structure conditioning agent is AlCl3、FeCl3, diethylenetriamine, ethylenediamine, in diethylamine
One or more, pore structure conditioning agent dosage are 1-5g/L.
In step (1), reacted under 2-4atm pressure condition, reaction temperature is 50-150 DEG C, reaction time 12-36
Hour；Deionized water is washed 3-5 times；Drying temperature is 40-90 DEG C, and drying time is 12-24 hours；Sintering temperature is 400-
700 DEG C, roasting time is 4-8 hours.
In step (2), the preparation method of titanium dioxide nanoparticle is as follows：By butyl titanate, absolute ethyl alcohol, concentrated nitric acid,
Modifying agent is soluble in water, stirs, and obtains milky white liquid, is evaporated to obtain titanium dioxide nanoparticle；
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, modifying agent, the mass ratio of water are 15-25:35-45:0.5-2:0.5-
1.5:45-75, described modifying agent are one or both of cerous nitrate or lanthanum nitrate.
Mixing speed is 300-400r/s, mixing time 10-30min；Evaporated temperature is 50-80 DEG C.
In step (2), silicone zeolite carrier, the mass ratio of titanium dioxide nanoparticle are 5-12:40-50；1-3atm's
Pressure condition pushes flakiness, wafer diameters 2-6cm, sheet thickness 1-5mm.
In step (2), sintering temperature is 450-600 DEG C, and roasting time is 4-8 hours；Silica gel soak time is 8-
20min；Drying temperature is 50-80 DEG C.
Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater of the present invention is used to contain
The processing of cyanogen waste water, comprises the following steps：Silica/nano titanium oxide/silicone zeolite composite is mixed with cyanide wastewater
Close, shake, filter in the case where hernia lamp source is irradiated.
Wherein：
The mass ratio of silica/nano titanium oxide/silicone zeolite composite and cyanide wastewater is 1-5:1000；Hernia lamp
The power of light source is 60-100W；The concussion time is 0.5-3 hours.
Compared to the waste water of other smelting industries, harmful constituent is complicated in cyanide wastewater, the heavy metal ion species such as Zn, Cu
It is more, Zn, Cu plasma and CN in addition-The complex of formation has stronger stability.Therefore, the material for Treatment of Cyanide-containing Wastewater
Free cyanogen, the cyanogen of complexing can not only be catalytically decomposed in material, can also adsorb various heavy metal ion.But due to weight in cyanide wastewater
The content of metal ion is different, and heavy metal ion content order is Cu in common cyanide wastewater>Zn, and general sorbing material counterweight
The adsorption capacity order of metal ion is Zn>Cu, cause Ni metal relative surplus.Even if using the side of increase sorbing material dosage
Method is up to standard to ensure each heavy metal components absorption, can not also realize and be adsorbed while each heavy metal components, so as to realize suction
The adsorption function of enclosure material maximizes.
The present invention is by the structure assembling modification to silica/nano titanium oxide/silicone zeolite composite, by activity
Group is incorporated on silicone zeolite carrier, so as to which cyanogen simultaneous selection absorption heavy metal be catalytically decomposed to reach the mesh of synchronous purification
's.Structure assembling modification needs to consider following factor：First, sorbing material is to free Cyanide in cyanide wastewater and complex cyanide
Catalytic decomposition ability and the degree of decomposition, second, in cyanide wastewater heavy metal ion species and content, third, sorbing material
Saturated adsorption capacity, absorption order, fourth, sorbing material catalytic decomposition and the cooperative effect of absorption and the optimization for the treatment of effect.
For factors above, modifying agent is optimized and configured, it is ensured that silica/nano titanium oxide/silicone zeolite composite wood
The adsorption function of material maximizes.
Beneficial effects of the present invention are as follows：
Silica/nano titanium oxide/silicone zeolite composite prepared by the present invention, have absorption and catalytic decomposition work(concurrently
Can, free Cyanide CN in cyanide wastewater-And complex cyanide [Cu (CN)6]4-Material surface is adsorbed to, under the irradiation of light source, is dissociated
Cyanogen and complex cyanide are decomposed under the catalytic action of nano titanium oxide, become nontoxic material, and zinc, copper heavy metal are then adsorbed to
Material surface, while realize effective degraded to cyanogen in cyanide wastewater and effective absorption of heavy metal ion.
The present invention is modified silicone zeolite by pore structure conditioning agent Al, Fe, amine, and silicon is adjusted in the presence of sodium hydroxide solution
The pore structure of zeolite, increase the surface area of silicone zeolite, meanwhile, Al, Fe, amine can change copper, zinc and silicone zeolite into bond energy
Power, enhance the absorption affinity of copper, zinc and silicone zeolite so that material can synchronous absorbing copper, zinc, improve material to copper, zinc
Adsorbance；Also by the way that cerous nitrate or lanthanum nitrate are added in butyl titanate, absolute ethyl alcohol, concentrated nitric acid solution, in generation nanometer
Directly will be nano-titanium dioxide modified during titanium dioxide, the electronics bond energy on nano titanium oxide track has been activated, has been protected
The modified effect of nano titanium oxide has been demonstrate,proved, has enhanced the catalytic decomposition ability to cyanogen；, will be modified again in the presence of silica gel
Titanium dioxide nanoparticle is loaded on modified silicone zeolite carrier, and it is multiple to obtain silica/nano titanium oxide/silicone zeolite
Condensation material.Average pore size, the specific surface area of silica/nano titanium oxide/silicone zeolite composite of the present invention become big,
Cyanogen that can be effectively in cyanide wastwater degradation, it is synchronous to adsorb different heavy metals.
The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 260-360m in the present invention2/ g,
Average pore size is 0.45-0.75nm；Its decomposition amount to cyanogen in cyanide wastewater is 311.2-322.9mg/g, and the adsorbance of copper is
402.1-440.3mg/g the adsorbance of zinc is 498.3-542.1mg/g.
Brief description of the drawings
Fig. 1 is the cyanogen root decomposition and inversion route map of the present invention；
Fig. 2 is the structural representation of silica/nano titanium oxide/silicone zeolite composite；
Fig. 3 is the TG-DTG images of silica/nano titanium oxide/silicone zeolite composite in embodiment 1；
Fig. 4 is the EDS figures of silica/nano titanium oxide/silicone zeolite composite.
A, the EDS figures of the material of comparative example 5；B, the EDS figures of the material of comparative example 4；C, the EDS figures of the material of embodiment 2；D, implement
The EDS figures of the material of example 6；E, the EDS figures of the material of embodiment 7；F, the EDS figures of the material of embodiment 8.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
(1) preparation of silicone zeolite carrier
It is 1 by mass ratio:4 silicone zeolite and sodium hydroxide solution mixing, is placed in three-necked flask, is placed in electric heating cover,
Stirred 36 hours at a temperature of 60 DEG C, it is pore structure conditioning agent that diethylenetriamine is added in whipping process, the dosage of diethylenetriamine
For 1g/L, synthesis modification silicone zeolite gel.
Modified silicon zeolite gel is put in the autoclave that pressure is 2atm, 100 DEG C of temperature of control, reaction 24 are small
When, filter, 3 times, again 80 DEG C dryings 12 hours are first washed with deionized, last 550 DEG C of roastings obtain being modified silicone zeolite for 4 hours
Carrier.
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, lanthanum nitrate is soluble in water, 30min is stirred under 300r/s rotating speeds, is obtained
Milky white liquid, it is evaporated to obtain titanium dioxide nanoparticle, wherein butyl titanate, absolute ethyl alcohol, concentrated nitric acid, nitric acid at 80 DEG C
Lanthanum, the mass ratio of water are 20:35:0.5:1:60.
It is 5 by mass ratio:45 modified silicon Zeolite support, titanium dioxide nanoparticle are well mixed, in 1atm pressure
Under the conditions of be pressed into a diameter of 2cm, thickness be 1mm thin slice, then thin slice is calcined 8 hours at 450 DEG C, in silica gel
10min is soaked, is finally dried in 80 DEG C of drying boxes, that is, obtains silica/nano titanium oxide/silicone zeolite composite.
The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 302.5m2/ g, average pore size 0.51nm.
The application of silica/nano titanium oxide/silicone zeolite composite：It is 1 by mass ratio:1000 titanium dioxide
Silicon/nano titanium oxide/silicone zeolite composite mixes with cyanide wastewater, shakes 3 under conditions of the irradiation of 100W hernias lamp source
Hour, filtering.
As shown in Fig. 2 the single molecule structure of silica/nano titanium oxide/silicone zeolite composite is as follows：Titanium dioxide
Silicon is coated on the outer surface of nano titanium oxide, and nano titanium oxide is fixedly connected on to the surface of silicone zeolite.
As shown in figure 3, the TG-DTG images of silica/nano titanium oxide/silicone zeolite composite.
Embodiment 2
(1) preparation of silicone zeolite carrier
It is 1 by mass ratio:2 silicone zeolite and sodium hydroxide solution mixing, is placed in three-necked flask, is placed in electric heating cover,
Stirred 32 hours at a temperature of 90 DEG C, AlCl is added in whipping process3As pore structure conditioning agent, AlCl3Dosage be 3g/L, close
Into modified silicon zeolite gel.
Modified silicon zeolite gel is put in the autoclave that pressure is 3atm, control temperature 60 C, reaction 35 hours,
Filter, 3 times, again 50 DEG C dryings 22 hours are first washed with deionized, last 450 DEG C of roastings obtain being modified silicone zeolite load for 8 hours
Body.
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, lanthanum nitrate is soluble in water, 25min is stirred under 400r/s rotating speeds, is obtained
Milky white liquid, it is evaporated to obtain titanium dioxide nanoparticle, wherein butyl titanate, absolute ethyl alcohol, concentrated nitric acid, nitric acid at 50 DEG C
Lanthanum, the mass ratio of water are 25:45:1:0.5:60.
It is 7 by mass ratio:42 modified silicon Zeolite support, titanium dioxide nanoparticle are well mixed, in 2atm pressure
Under the conditions of be pressed into a diameter of 3cm, thickness be 3mm thin slice, then thin slice is calcined 6 hours at 500 DEG C, in silica gel
15min is soaked, is finally dried in 70 DEG C of drying boxes, that is, obtains silica/nano titanium oxide/silicone zeolite composite.
The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 350.8m2/ g, average pore size 0.63nm.
The application of silica/nano titanium oxide/silicone zeolite composite：It is 3 by mass ratio:1000 titanium dioxide
Silicon/nano titanium oxide/silicone zeolite composite mixes with cyanide wastewater, and concussion 2 is small under conditions of the irradiation of 60W hernias lamp source
When, filtering.
Silica/nano titanium oxide/silicone zeolite composite is subjected to EDS detections, sees c in Fig. 4.
Embodiment 3
(1) preparation of silicone zeolite carrier
It is 1 by mass ratio:5 silicone zeolite and sodium hydroxide solution mixing, is placed in three-necked flask, is placed in electric heating cover,
Stirred 30 hours at a temperature of 120 DEG C, FeCl is added in whipping process3As pore structure conditioning agent, FeCl3Dosage be 5g/L, close
Into modified silicon zeolite gel.
Modified silicon zeolite gel is put in the autoclave that pressure is 3.5atm, 80 DEG C of temperature of control, reaction 30 are small
When, filter, 4 times, again 60 DEG C dryings 20 hours are first washed with deionized, last 600 DEG C of roastings obtain modified silicon boiling for 6.5 hours
Stone carrier.
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, lanthanum nitrate is soluble in water, 20min is stirred under 350r/s rotating speeds, is obtained
Milky white liquid, it is evaporated to obtain titanium dioxide nanoparticle, wherein butyl titanate, absolute ethyl alcohol, concentrated nitric acid, nitric acid at 60 DEG C
Lanthanum, the mass ratio of water are 15:40:1.5:1.5:60.
It is 8 by mass ratio:50 modified silicon Zeolite support, titanium dioxide nanoparticle are well mixed, in 2.5atm pressure
A diameter of 4cm is pressed under the conditions of power, the thin slice that thickness is 2mm, be then calcined thin slice 5 hours at 550 DEG C, then at silica gel
Middle immersion 18min, is finally dried in 55 DEG C of drying boxes, that is, obtains silica/nano titanium oxide/silicone zeolite composite wood
Material.The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 332.4m2/ g, average pore size are
0.55nm。
The application of silica/nano titanium oxide/silicone zeolite composite：It is 5 by mass ratio:1000 titanium dioxide
Silicon/nano titanium oxide/silicone zeolite composite mixes with cyanide wastewater, is shaken under conditions of the irradiation of 100W hernias lamp source
2.5 hours, filtering.
Embodiment 4
(1) preparation of silicone zeolite carrier
It is 1 by mass ratio:7 silicone zeolite and sodium hydroxide solution mixing, is placed in three-necked flask, is placed in electric heating cover,
Stirred 20 hours at a temperature of 150 DEG C, AlCl is added in whipping process3、FeCl3As pore structure conditioning agent, AlCl3、FeCl3's
Dosage is 2g/L, and both mass ratioes are 1:1, synthesis modification silicone zeolite gel.
Modified silicon zeolite gel is put in the autoclave that pressure is 4atm, 120 DEG C of temperature of control, reaction 20 are small
When, filter, 3 times, again 75 DEG C dryings 16 hours are first washed with deionized, last 650 DEG C of roastings obtain being modified silicone zeolite for 5 hours
Carrier.
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, cerous nitrate is soluble in water, 15min is stirred under 380r/s rotating speeds, is obtained
Milky white liquid, it is evaporated to obtain titanium dioxide nanoparticle, wherein butyl titanate, absolute ethyl alcohol, concentrated nitric acid, nitric acid at 70 DEG C
Cerium, the mass ratio of water are 25:35:0.5:1:55.
It is 10 by mass ratio:47 modified silicon Zeolite support, titanium dioxide nanoparticle are well mixed, in 3atm pressure
Under the conditions of be pressed into a diameter of 4cm, thickness be 5mm thin slice, then thin slice is calcined 7 hours at 550 DEG C, in silica gel
20min is soaked, is finally dried in 65 DEG C of drying boxes, that is, obtains silica/nano titanium oxide/silicone zeolite composite.
The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 352.8m2/ g, average pore size 0.65nm.
The application of silica/nano titanium oxide/silicone zeolite composite：It is 4 by mass ratio:1000 titanium dioxide
Silicon/nano titanium oxide/silicone zeolite composite mixes with cyanide wastewater, shakes 1.5 under conditions of the irradiation of 85W hernias lamp source
Hour, filtering.
Embodiment 5
(1) preparation of silicone zeolite carrier
It is 1 by mass ratio:9 silicone zeolite and sodium hydroxide solution mixing, is placed in three-necked flask, is placed in electric heating cover,
Stirred 15 hours at a temperature of 190 DEG C, ethylenediamine is added in whipping process as pore structure conditioning agent, the dosage of ethylenediamine is 4g/
L, synthesis modification silicone zeolite gel.
Modified silicon zeolite gel is put in the autoclave that pressure is 2.5atm, 100 DEG C of temperature of control, reaction 24 are small
When, filter, 5 times, again 90 DEG C dryings 14 hours are first washed with deionized, last 700 DEG C of roastings obtain being modified silicone zeolite for 4 hours
Carrier.
(2) preparation of silica/nano titanium oxide/silicone zeolite composite
Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, lanthanum nitrate is soluble in water, 10min is stirred under 360r/s rotating speeds, is obtained
Milky white liquid, it is evaporated to obtain titanium dioxide nanoparticle, wherein butyl titanate, absolute ethyl alcohol, concentrated nitric acid, nitric acid at 65 DEG C
Lanthanum, the mass ratio of water are 20:35:2:1:75.
It is 12 by mass ratio:45 modified silicon Zeolite support, titanium dioxide nanoparticle are well mixed, in 1.5atm pressure
A diameter of 5cm is pressed under the conditions of power, the thin slice that thickness is 3mm, be then calcined thin slice 4.5 hours at 600 DEG C, then at silicon
16min is soaked in glue, is finally dried in 70 DEG C of drying boxes, that is, obtains silica/nano titanium oxide/silicone zeolite composite wood
Material.The specific surface area of silica/nano titanium oxide/silicone zeolite composite is 298.7m2/ g, average pore size are
0.72nm。
The application of silica/nano titanium oxide/silicone zeolite composite：It is 2 by mass ratio:1000 titanium dioxide
Silicon/nano titanium oxide/silicone zeolite composite mixes with cyanide wastewater, and concussion 1 is small under conditions of the irradiation of 90W hernias lamp source
When, filtering.
Embodiment 6
According to the method for embodiment 2, the difference is that：10min is soaked in silica gel, remaining step such as embodiment 2.By dioxy
SiClx/nano titanium oxide/silicone zeolite composite carries out EDS detections, sees d in Fig. 4.
Embodiment 7
According to the method for embodiment 2, the difference is that：10min, butyl titanate, absolute ethyl alcohol, dense nitre are soaked in silica gel
Acid, lanthanum nitrate, the mass ratio of water are 20:35:0.5:1:60, remaining step such as embodiment 2.By silica/nanometer titanium dioxide
Titanium/silicone zeolite composite carries out EDS detections, sees e in Fig. 4.
Embodiment 8
According to the method for embodiment 2, the difference is that：Thin slice is calcined 8 hours at 450 DEG C, remaining step such as embodiment
2.Silica/nano titanium oxide/silicone zeolite composite is subjected to EDS detections, sees f in Fig. 4.
Comparative example 1
In the step of embodiment 1 (1), pore structure conditioning agent is not added with when preparing modified silicon Zeolite support, other steps are equal
It is same as Example 1.Wherein, the specific surface area of silica/nano titanium oxide/silicone zeolite composite is 185m2/ g, put down
Equal aperture is 0.3nm.
Comparative example 2
In the step of embodiment 1 (1), modified silicon Zeolite support direct impregnation silica gel, other steps with the phase of embodiment 1
Together.
Test result indicates that nano titanium oxide load factor is relatively low, the decomposition amount of cyanogen directly affects.Wherein, titanium dioxide
The specific surface area of silicon/nano titanium oxide/silicone zeolite composite is 231m2/ g, average pore size 0.40nm.
Comparative example 3
In the step of embodiment 1 (2), when preparing titanium dioxide nanoparticle, according to Chinese patent CN105749857A
The step of embodiment 1 (1), prepares to the method for step (3), and other steps are identical with the embodiment of the present invention 1.Wherein, titanium dioxide
The specific surface area of silicon/nano titanium oxide/silicone zeolite composite is 249m2/ g, average pore size 0.35nm.
Comparative example 4
According to the method for embodiment 2, the difference is that：20min, AlCl are soaked in silica gel3Dosage be 4g/L, and do not add
Add modifying agent lanthanum nitrate, remaining step such as embodiment 2.Silica/nano titanium oxide/silicone zeolite composite is carried out
EDS is detected, and sees b in Fig. 4.
Comparative example 5
According to the method for embodiment 2, the difference is that：Titanium dioxide nanoparticle is not added, 20min is soaked in silica gel,
Remaining step such as embodiment 2.Silica/nano titanium oxide/silicone zeolite composite is subjected to EDS detections, sees a in Fig. 4.
Analyze the catalysis of silica/nano titanium oxide/silicone zeolite composite in embodiment 1-5 and comparative example 1-3
Adsorption effect, as shown in table 1.
The catalytic adsorption effect of 1 silica of table/nano titanium oxide/silicone zeolite composite
Claims (10)
- A kind of 1. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater, it is characterised in that：It is made Preparation Method comprises the following steps：(1) preparation of silicone zeolite carrierSilicone zeolite is mixed with sodium hydroxide solution, adding hole structure regulator, synthesize silicone zeolite gel, reacted, filtering, washed Wash, dry, roasting, obtain silicone zeolite carrier；(2) preparation of silica/nano titanium oxide/silicone zeolite compositeSilicone zeolite carrier, titanium dioxide nanoparticle are well mixed, are pressed into thin slice, is calcined, silica gel immersion, drying, obtains two Silica/nano titanium oxide/silicone zeolite composite.
- 2. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 1, It is characterized in that：In step (1), the mass ratio of silicone zeolite and sodium hydroxide solution is 1:2-9；The adding hole under conditions of stirring Structure regulator, described whipping temp is 50-200 DEG C, mixing time is 12-36 hours；Described pore structure conditioning agent is AlCl3、FeCl3, diethylenetriamine, ethylenediamine, the one or more in diethylamine, hole Structure regulator dosage is 1-5g/L.
- 3. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 1, It is characterized in that：In step (1), reacted under 2-4atm pressure condition, reaction temperature is 50-150 DEG C, and the reaction time is 12-36 hours；Deionized water is washed 3-5 times；Drying temperature is 40-90 DEG C, and drying time is 12-24 hours；Sintering temperature is 400-700 DEG C, roasting time is 4-8 hours.
- 4. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 1, It is characterized in that：In step (2), the preparation method of titanium dioxide nanoparticle is as follows：By butyl titanate, absolute ethyl alcohol, dense nitre Acid, modifying agent are soluble in water, stir, obtain milky white liquid, are evaporated to obtain titanium dioxide nanoparticle.
- 5. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 4, It is characterized in that：Butyl titanate, absolute ethyl alcohol, concentrated nitric acid, modifying agent, the mass ratio of water are 15-25:35-45:0.5-2:0.5- 1.5:45-75, described modifying agent are one or both of cerous nitrate or lanthanum nitrate.
- 6. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 4, It is characterized in that：Mixing speed is 300-400r/s, mixing time 10-30min；Evaporated temperature is 50-80 DEG C.
- 7. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 1, It is characterized in that：In step (2), silicone zeolite carrier, the mass ratio of titanium dioxide nanoparticle are 5-12:40-50；In 1-3atm Pressure condition push flakiness, wafer diameters 2-6cm, sheet thickness 1-5mm.
- 8. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 1, It is characterized in that：In step (2), sintering temperature is 450-600 DEG C, and roasting time is 4-8 hours；Silica gel soak time is 8- 20min；Drying temperature is 50-80 DEG C.
- 9. a kind of silica/nano titanium oxide/silicone zeolite of any described Treatment of Cyanide-containing Wastewater of claim 1-8 is compound The application of material, it is characterised in that：For the processing of cyanide wastewater, comprise the following steps：By silica/nanometer titanium dioxide Titanium/silicone zeolite composite mixes with cyanide wastewater, shakes, filters under conditions of the irradiation of hernia lamp source.
- 10. silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater according to claim 9 Application, it is characterised in that：The mass ratio of silica/nano titanium oxide/silicone zeolite composite and cyanide wastewater is 1- 5:1000；The power of hernia lamp source is 60-100W；The concussion time is 0.5-3 hours.
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| CN113058539A (en) * | 2021-03-29 | 2021-07-02 | 山东理工大学 | Mn and N co-doped silicon-based nano TiO2Preparation method and application of material |
| CN113058581A (en) * | 2021-03-29 | 2021-07-02 | 山东理工大学 | Ammonium salt-silicon modified silicon-based nano-particlesTiO2Preparation method and application of material |
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| CN113058581A (en) * | 2021-03-29 | 2021-07-02 | 山东理工大学 | Ammonium salt-silicon modified silicon-based nano-particlesTiO2Preparation method and application of material |
| CN113058581B (en) * | 2021-03-29 | 2022-12-16 | 山东理工大学 | Ammonium salt-silicon modified silicon-based nano-particlesTiO 2 Preparation method and application of material |
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