CN109046441A - A kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst and preparation method thereof - Google Patents
A kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst and preparation method thereof Download PDFInfo
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- CN109046441A CN109046441A CN201811072067.0A CN201811072067A CN109046441A CN 109046441 A CN109046441 A CN 109046441A CN 201811072067 A CN201811072067 A CN 201811072067A CN 109046441 A CN109046441 A CN 109046441A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 8
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000013335 mesoporous material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000006477 desulfuration reaction Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- -1 corrosion-resistant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
Abstract
The invention discloses a kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalysts and preparation method thereof.The photochemical catalyst includes following components by weight percent: 85-90 parts of catalyst carrier, 10-15 parts of sodium metasilicate, 5-10 parts of anatase phase titanium dioxide, 0.5-2.0 parts of graphite phase carbon nitride.Preparation method is as follows: (1) catalyst carrier Cu-ZSM-5 washing, drying is stand-by；(2) TiO is prepared by titanium source of butyl titanate2Presoma；(3) by the TiO of preparation2Presoma is uniformly mixed with Cu-ZSM-5 and is dried after 0.5 ~ 1h of ultrasound；(4) product after drying in step (3) is uniformly mixed with graphite phase carbon nitride presoma, is roasted using an one-step baking method.(5) product of roasting in step (4) is soaked with sodium silicate solution, pressing mold molding obtains molding TiO after drying2/g‑C3N4/ Cu-ZSM-5 photochemical catalyst.The present invention loads anatase phase titanium dioxide using doping vario-property molecular sieve as carrier, by sol-gel method, and doped graphite phase carbon nitride improves the photocatalysis denitrification efficiency of catalyst by the synergistic effect of the two.
Description
Technical field
The present invention relates to a kind of preparation methods of photochemical catalyst, more particularly to one kind for removing in flue gas
SO2, the photochemical catalyst of NOx and preparation method thereof, belong to environmental protection technical field.
Background technique
With the increase of industrial development and motor vehicles, oxysulfide (SOx), nitrogen oxides (NOx) and work
The discharge of industry exhaust gas VOCs rises year by year, and brings serious harm to natural environment and human lives.In recent years, China is original
" Industrial " three Waste " discharge tentative standard " exhaust gas section and the basis in relation to other professional countries atmosphere pollutants emission standards
On, more stringent waste gas emission standard has been formulated, desulphurization denitration technology and industrial gas emission have been put forward new requirements.
Currently, China industrially apply it is more for wet process (lime-gypsum) desulfurization and SCR denitration.Both skills
Art had evolved into desulphurization denitration field it is ripe, but also there are many shortcoming:
1) mineral products gypsum in China's has low cost, the advantage of high quality, and the by-product gypsum in process of wet desulphurization does not have
Commercial value is merely able to abandon accumulation processing.Meanwhile the desulfuration efficiency of lime stone-gypsum method is difficult to meet existing desulfurization standard,
Cascade towers desulfurization is needed, causes investment big, operating cost is high.
2) on April 22nd, 2016, China in New York endorsed " Paris agreement " for CO2Discharge have new requirement.And
Wet desulphurization handles SO2A large amount of CO is discharged in the process2, this is disagreed with " Paris agreement " content.
3) very widely used today V2O5/TiO2Catalyst has the shortcomings that easy to wear, easy poisoning, is not solved yet so far
Certainly.
4) SCR technology is by NH3As reactant, and NH3Consumption mass energy is needed in the synthesis process, when this does not meet new
For the requirement of Green Chemistry.
Photocatalytic oxidation be mainly in flue gas NOx and SOx be oxidized to NO under excess oxygen2With SO3, can also incite somebody to action
Part NO photo catalytic reduction is decomposed into N2And O2, then removing achieved the purpose that by the methods of spray washing.Li Chunhu etc. is led herein
Domain has been instructed to complete several papers written by postgraduates, such as " metal and nonmetallic modifying TiO2The preparation of/ASC photochemical catalyst and NO are aoxidized
Surface photoelectron behavioral study " (doctor's thesis, 2015), " naval vessel flue gas photochemical catalytic oxidation cooperates with Absorption by Sea Water desulfurization
Denitration technology research " (master's thesis, 2017).Molecular sieve have special cellular structure, great specific surface area, often
The features such as warm high stability down, so that molecular sieve is applied as catalyst in catalytic field or all has pole as catalyst carrier
Big application prospect.
Currently, the catalyst research of photocatalytic redox method is concentrated mainly on g-C3N4、TiO2And metal oxide.And
The carrier of photochemical catalyst selects main active charcoal, ceramics, active carbocoal and molecular sieve etc..TiO2With g-C3N4By its property
The features such as stable, at low cost, the nontoxic and service life is long has been a concern in photocatalysis field.TiO2With g-C3N4There is band
Gap is wider, and quantum efficiency is low, and the limitations such as the recombination rate height in electronics and hole, this leads to the TiO of single load2With g-C3N4Light
The catalytic efficiency of catalyst is lower.Current existing photochemical catalyst often due to preparation condition is complicated, urge by the light after leading to volume production
There is the problems such as active component reunites, is not strong for load solid in agent, so that its practical catalytic efficiency differs larger with ideal value.How
Simplify preparation process and improve load rear catalyst activity, load fastness is always that people make great efforts the problem captured.
Summary of the invention
In view of the above-mentioned problems, a kind of it is an object of that present invention to provide preparation methods simple, desulphurization denitration high catalytic efficiency, negative
It is loaded solid solid, corrosion-resistant, titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst that plasticity is good and preparation method thereof.
The present invention is with ZSM-5, AlPO4- 11 grades or its doping vario-property molecular sieve are carrier, are loaded by sol-gel method
Anatase phase titanium dioxide (the TiO of highlight catalytic active2), and it is doped with high-specific surface area and electricity simultaneously in loading process
Graphite phase carbon nitride (the g-C of sub- transmission rate3N4), by the synergistic effect of two kinds of high efficiency photocatalysts, reduce electronics and sky
Cave it is compound, improve the photocatalysis denitrification efficiency of catalyst.
Photochemical catalyst of the present invention includes following components by weight percent: 85-90 parts of catalyst carrier, 10-15 parts of sodium metasilicate,
Anatase phase titanium dioxide (TiO2) 5-10 parts, graphite phase carbon nitride (g-C3N4) 0.5-2.0 parts.
The catalyst carrier is the molecular sieve or other metal-doped modified micro- mesoporous materials after Cu doping vario-property.
Molecular sieve after the Cu doping vario-property is Cu-ZSM-5.
The silica alumina ratio of the Cu-ZSM-5 is 40-100, bulk density 1.3-1.6g/cm3。
The catalyst activity component is anatase phase titanium dioxide (TiO2) doped graphite phase carbon nitride (g-C3N4)。
The catalyst activity component completes load in loading process for a step.
The preparation method of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst of the present invention, includes the following steps:
(1) catalyst carrier Cu-ZSM-5 washing, drying is stand-by；
(2) TiO is prepared by titanium source of butyl titanate2Presoma；
(3) by the TiO of preparation2Presoma is uniformly mixed with Cu-ZSM-5 and is dried after 0.5~1h of ultrasound；
(4) Cu-ZSM-5 obtained after drying in step (3) is uniformly mixed with graphite phase carbon nitride presoma, passes through one
One-step baking method roasts it
(5) product of roasting in step (4) is soaked with sodium silicate solution, pressing mold molding stands overnight, obtains into after drying
TiO after type2/g-C3N4/ Cu-ZSM-5 photochemical catalyst.
Washing is successively using 0.01mol/L sodium nitrate solution and deionized water in the step (1).
Drying temperature is 105~130 DEG C in the step (1).
TiO is prepared in the step (2)2The formula of presoma is four fourth vinegar of metatitanic acid: acetic acid: the volume ratio of deionized water is
1:(0.05~0.1): (0.05~0.1).
Drying temperature is 105~130 DEG C in the step (3).
The Cu-ZSM-5 and graphite phase carbon nitride presoma mixing mass ratio obtained after drying in the step (4) is 1.0:
(0.2~0.4).
Graphite phase carbon nitride presoma is melamine, urea or cyanuric acid in the step (4).
An one-step baking method is process control 3~8 DEG C/min of heating in the step (4), rises to 250~300 DEG C by room temperature
And 0.5~1h of constant temperature, then 500~600 DEG C are warming up to, and 1.5~2.5h of constant temperature.
Sodium silicate solution concentration is 0.5~0.8mol/L in the step (5), and drying temperature is 70~90 DEG C.
Compared with prior art, the present invention has the advantage that
(1) carrier that the present invention selects is the ZSM-5 after Cu doping vario-property, which has ten-ring two-dimensional framework knot
Structure, specific surface area is larger, good to the absorption property of NOx, and lattice defect is more；
(2) present invention has loaded anatase phase titanium dioxide on the ZSM-5 after Cu doping vario-property and has been doped with graphite-phase
The total catalytic effect of carbonitride, two kinds of catalyst improves the efficiency of catalyst photocatalysis desulphurization denitration；
(3) present invention by loading the total catalytic action of anatase phase titanium dioxide and graphite phase carbon nitride altogether, so that making
Standby properties of catalyst is improved；
(4) present invention passes through an one-step baking method for TiO during the preparation process2Presoma and g-C3N4Presoma is converted into light
Catalytic active component simplifies operating process, reduces the production cost；
(5) photochemical catalyst prepared by the present invention improves catalyst strength by the way that sodium metasilicate is added, can be with after pressing mold molding
Meet various reactor requirements；
(6) all kinds of gas cleanings and industrial waste gas VOCs purified treatment be the composite can be widely applied to, flue gas desulfurization is solved
Denitration problem, and the present invention has the characteristics that nontoxic, environmentally friendly, meets the policy requirements of national green environmental protection.
Detailed description of the invention
Fig. 1 is TiO prepared by the present invention2/g-C3N4The XRD spectra of/Cu-ZSM-5 photochemical catalyst.
Fig. 2 is the figure that the sample of embodiment 1 is shot under 50 times of electron microscopes.
Fig. 3 is the figure that the sample of embodiment 1 is shot under 500 times of electron microscopes.
Specific embodiment
The present invention is described in further detail below with reference to embodiment and comparative example.It should be appreciated that implementation of the invention is not
The following examples are confined to, the accommodation in any form or change made to the present invention fall within present invention protection model
It encloses.In the present invention, all equipment and raw material etc. are commercially available or the industry is common.In following embodiments
Method is unless otherwise instructed the conventional method of this field.
Embodiment 1:
(1) by 100g Cu-ZSM-5 successively with the sodium nitrate solution of 0.01mol/L, deionized water washing, suction filtration, 105 DEG C
Drying is stand-by.
(2) 25mL ethyl alcohol is taken, 7mL butyl titanate is added dropwise into dehydrated alcohol and stirs 30min, A liquid is denoted as, takes
15ml dehydrated alcohol sequentially adds 3mL acetic acid, 1mL deionized water thereto and stirs, and A liquid is slowly added into above-mentioned solution
In, TiO is obtained after still aging2Presoma.
(3) by the TiO of preparation2Presoma is uniformly mixed with Cu-ZSM-5 and 105~130 DEG C of drying after ultrasound 30min.
(4) it by the obtained Cu-ZSM-5 after drying, is uniformly mixed with 20g melamine.
(5) mixing rear catalyst is placed in tube furnace, is heated up by process control, heating rate is 3 DEG C/min, by room
Temperature rise is to 250 DEG C, after constant temperature 1h, then with 3 DEG C/min rate rises to 500 DEG C, 500 DEG C of constant temperature 2h are slowly cooled to room temperature.
(6) it is soaked with the sodium silicate solution of 0.73mol/L, the molding of tablet press machine 1.0MPa pressing mold is placed at room temperature for after 12h 80 DEG C
Drying 12h obtains finished catalyst: TiO2/g-C3N4/ Cu-ZSM-5, is denoted as 1-Cu/Ti-CN.(note: 1 represents an one-step baking method
Obtained catalyst)
TiO prepared by embodiment 12/g-C3N4The XRD spectra of/Cu-ZSM-5 photochemical catalyst is as shown in Figure 1, can be with from figure
Find out that sample shows the characteristic diffraction peak of Cu-ZSM-5, and each characteristic peak does not show to deviate because of the doping of Cu, this
It is only to be had an impact to few partial crystals pattern, because Cu doping is seldom so each ZSM-5 diffraction maximum does not occur partially
It moves；TiO2With g-C3N4Load capacity is all less, so its characteristic peak is weaker in XRD spectra, being 13.6 ° in the angle of diffraction, there are g-
C3N4Characteristic peak (marks 1) in figure, show anatase TiO at 48.0 °2(101) crystal face characteristic peak (3 are marked in figure),
25.3 ° nearby there is g-C3N4With TiO2(110) crystal face feature overlap peak (2 are marked in figure).It proves successfully to exist by one-step method
TiO has been loaded on Cu-ZSM-52With g-C3N4, and TiO2It shows as the higher anatase crystal of incident photon-to-electron conversion efficiency.
The pattern of sample prepared by embodiment 1 is as shown in Figures 2 and 3, and as can be seen from the figure Cu-ZSM-5 shows good
Good crystal complexion, the catalyst of load are more evenly distributed in carrier surface, do not occur agglomeration.
Comparative example 1:
(1) by 100g Cu-ZSM-5 successively with the sodium nitrate solution of 0.01mol/L, deionized water washing, suction filtration, 105 DEG C
Drying is stand-by.
(2) 25mL ethyl alcohol is taken, 7mL butyl titanate is added dropwise into dehydrated alcohol and stirs 30min, A liquid is denoted as, takes
15ml dehydrated alcohol sequentially adds 3mL acetic acid, 1mL deionized water thereto and stirs, and A liquid is slowly added into above-mentioned solution
In, TiO is obtained after still aging2Presoma.
(3) by the TiO with 1 moderate of embodiment2Presoma is placed in a beaker, 105~130 DEG C of drying after ultrasonic 30min.
(4) by with the melamine of 1 moderate of embodiment, ultrasound after TiO2Presoma, Cu-ZSM-5 are sequentially placed into tubular type
In furnace, by temperature programmed control, heating rate is 3 DEG C/min, 250 DEG C is risen to by room temperature, after constant temperature 1h, then with 3 DEG C/min rate
500 DEG C are risen to, 500 DEG C of constant temperature 2h are slowly cooled to room temperature, finally obtain g-C3N4、TiO2、Cu-ZSM-5。
(5) by the g-C of preparation3N4、TiO2, Cu-ZSM-5 agate alms bowl ground and mixed.
(6) mixed catalyst, the molding of tablet press machine 1.0MPa pressing mold, room are soaked with the sodium silicate solution of 0.73mol/L
80 DEG C of drying 12h obtain finished catalyst after temperature places 12h, and being denoted as J-Cu/Ti-CN, (note: what J represented that mechanical mixture obtains urges
Agent).
The 1-Cu/Ti-CN catalyst of the preparation of embodiment 1 and the J-Cu/ of the direct mechanical mixture of comparative example 1 preparation is respectively adopted
Ti-CN catalyst carries out the assessment of photocatalysis sea water desulfuration denitration performance, evaluating conditions are as follows: under ultraviolet lighting, cigarette is simulated in import
SO in gas2、NO、O2And H2The concentration of O is respectively 800~2000mg/m3, 350~450mg/m3, 20% and 10%, mixed airflow
Amount is 2L/min, and reaction temperature is 50~70 DEG C, and reactor bed loading catalyst is 150mL, built in type ultraviolet lamp or mercury lamp
For 150W, wavelength 254nm, at the same by the flow of 10L/h into photo catalysis reactor sprayed sea water.Evaluating result is shown in Table 1.
1 comparative example 1 of table carries out sea water desulfuration denitration performance evaluating result with 1 photochemical catalyst of embodiment
As can be seen from Table 1, with 1 mechanical mixture TiO of comparative example2、g-C3N4, Cu-ZSM-5 preparation catalyst compare, it is real
Apply the TiO of the preparation of example 12/g-C3N4/ Cu-ZSM-5 photochemical catalyst desulphurization denitration rate has a distinct increment, in different temperature conditions
Under, using TiO prepared by the present invention2/g-C3N4/ Cu-ZSM-5 photochemical catalyst, photocatalysis desulphurization denitration rate are much higher than direct machine
The catalyst that tool is mixed with is about high by 9%.Meanwhile reactor temperature also will affect its photocatalysis performance.With temperature liter
Height, denitrification rate increase, and desulfurization degree reduces.In optimal conditions, desulfurization degree is up to 98.9%, and denitrification rate is up to 95.3%.
Embodiment 2:
(1) by 100g Cu-ZSM-5 successively with the sodium nitrate solution of 0.01mol/L, deionized water washing, suction filtration, 105 DEG C
Drying is stand-by.
(2) 25mL ethyl alcohol is taken, 7mL butyl titanate is added dropwise into dehydrated alcohol and stirs 30min, A liquid is denoted as, takes
15ml dehydrated alcohol sequentially adds 3mL acetic acid, 1mL deionized water thereto and stirs, and A liquid is slowly added into above-mentioned solution
In, TiO is obtained after still aging2Presoma.
(3) by the TiO of preparation2Presoma is uniformly mixed with Cu-ZSM-5,20g urea and ultrasound 30min.
(4) catalyst after ultrasound is dried in 105~130 DEG C.
(5) catalyst is placed in tube furnace, by temperature programmed control, heating rate is 3 DEG C/min, extremely by room temperature
250 DEG C, after constant temperature 1h, then with 3 DEG C/min rate 500 DEG C are risen to, 500 DEG C of constant temperature 2h are slowly cooled to room temperature.
(6) it is soaked with the sodium silicate solution of 0.73mol/L, the molding of tablet press machine 1MPa pressing mold, is placed at room temperature for 80 DEG C of bakings after 12h
Dry 12h obtains finished catalyst, is denoted as 1*-Cu/Ti-CN.
Comparative example 2:
(1) by 100g Cu-ZSM-5 successively with the sodium nitrate solution of 0.01mol/L, deionized water washing, suction filtration, 105 DEG C
Drying is stand-by.
(2) 25mL ethyl alcohol is taken, four fourth rouge of 7mL metatitanic acid is added dropwise into dehydrated alcohol and stirs 30min, A liquid is denoted as, takes
15ml dehydrated alcohol sequentially adds 3mL acetic acid, 1mL deionized water thereto and stirs, and A liquid is slowly added into above-mentioned solution
In, TiO is obtained after still aging2Presoma.
(3) by the TiO of preparation2Presoma uniformly mixed with Cu-ZSM-5 and ultrasound 30min after 105~130 DEG C dry,
250 DEG C of 0.5~1h of roasting, 500 DEG C of 1~1.5h of roasting.
(4) the obtained Cu-ZSM-5 after roasting is taken uniformly to mix with 2 moderate urea of embodiment.
(5) mixture is placed in tube furnace, by temperature programmed control, heating rate is 3 DEG C/min, extremely by room temperature
250 DEG C, after constant temperature 1h, then with 3 DEG C/min rate 500 DEG C are risen to, constant temperature 2h is slowly cooled to room temperature.
(6) it is soaked with the sodium silicate solution of 0.73mol/L, the molding of tablet press machine 1.0MPa pressing mold is placed at room temperature for after 12h 80 DEG C
Drying 12h obtains finished catalyst, is denoted as 2-Cu/Ti-CN.(2 represent the catalyst by double roasting preparation)
Double roasting system is passed through by the 1*-Cu/Ti-CN catalyst of precursor preparation and comparative example 2 of urea to embodiment 2
Standby 2-Cu/Ti-CN catalyst carries out the assessment of photocatalysis sea water desulfuration denitration performance, evaluating conditions are as follows: under ultraviolet lighting, into
SO in mouth simulated flue gas2、NO、O2And H2The concentration of O is respectively 800~2000mg/m3, 350~450mg/m3, 20% and 10%,
Mixed gas flow is 2L/min, and reaction temperature is 50~70 DEG C, and reactor bed loading catalyst is 150mL, in wavelength 254nm
Dress type ultraviolet lamp or mercury lamp are 150W, meanwhile, by the flow of 10L/h into photo catalysis reactor sprayed sea water.Evaluating result is shown in
Table 2.
2 embodiment 2 of table carries out sea water desulfuration denitration performance evaluating result with comparative example photochemical catalyst
As can be seen from Table 2, the photochemical catalyst (1*-Cu/Ti-CN) that in embodiment 2 prepared by an one-step baking method is in photocatalysis
The photochemical catalyst (2-Z/Ti-CN) that in comparative example 2 prepared by substep roasting method is apparently higher than in desulphurization denitration performance, this is because point
The photochemical catalyst of one-step baking method preparation, will lead to TiO in second of roasting process2Crystal form changes, and leads to its catalytic
It can reduce.(1-Cu/Ti-CN) prepared by comparative example 1, (1*-Cu/Ti-CN) photocatalysis desulphurization denitration prepared by embodiment 2
Performance slightly reduces, this is because the presoma of the graphite phase carbon nitride used in embodiment 2 is urea, urea is converted into graphite
Phase carbon nitride process conversion ratio is low.So graphite phase carbon nitride doping in (1*-Cu/Ti-CN) photochemical catalyst prepared by embodiment 2
It measures less, causes catalytic performance slightly lower.
The above embodiments merely illustrate the technical concept and features of the present invention, is not intended to limit protection scope of the present invention.It is all
Any equivalent transformation or modification made according to the spirit of the present invention, should all cover in its protection scope.
Claims (10)
1. a kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst, it is characterised in that include following components by weight percent: catalyst
85-90 parts of carrier, 10-15 parts of sodium metasilicate, 5-10 parts of anatase phase titanium dioxide, 0.5-2.0 parts of graphite phase carbon nitride.
2. photochemical catalyst as described in claim 1, it is characterised in that the catalyst carrier is the molecule after Cu doping vario-property
Sieve or other metal-doped modified micro- mesoporous materials.
3. photochemical catalyst as claimed in claim 2, it is characterised in that the molecular sieve after the Cu doping vario-property is Cu-ZSM-5.
4. photochemical catalyst as claimed in claim 3, it is characterised in that the silica alumina ratio of the Cu-ZSM-5 is 40-100, accumulation
Density is 1.3-1.6g/cm3。
5. titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst preparation method described in a kind of claim 1, it is characterised in that
Include the following steps: that (1) is stand-by by catalyst carrier Cu-ZSM-5 washing, drying；(2) it is prepared by titanium source of butyl titanate
TiO2Presoma；(3) by the TiO of preparation2Presoma is uniformly mixed with Cu-ZSM-5 and is dried after ultrasound 0.5-1h；(4) by step
(3) Cu-ZSM-5 obtained after drying in is uniformly mixed with graphite phase carbon nitride presoma, is carried out by an one-step baking method to it
Roasting is to get TiO2/g-C3N4/ Cu-ZSM-5 photochemical catalyst.
6. the preparation method of photochemical catalyst as claimed in claim 5, feature is further comprising the steps of: by roasting in step (4)
It burns product to be soaked with sodium silicate solution, pressing mold molding stands overnight, photochemical catalyst after molding is obtained after drying.
7. the preparation method of photochemical catalyst as claimed in claim 5, it is characterised in that obtained after drying in the step (4)
Cu-ZSM-5 and graphite phase carbon nitride presoma mixing mass ratio are 1.0:(0.2-0.4).
8. the preparation method of photochemical catalyst as claimed in claim 5, it is characterised in that the graphite phase carbon nitride presoma is three
Poly cyanamid, urea or cyanuric acid.
9. the preparation method of photochemical catalyst as claimed in claim 5, it is characterised in that an one-step baking method is journey in the step (4)
Sequence control 3-8 DEG C/min of heating, rises to 250-300 DEG C and constant temperature 0.5-1h by room temperature, then be warming up to 500-600 DEG C, and constant temperature
1.5~2.5h。
10. the preparation method of photochemical catalyst as claimed in claim 6, it is characterised in that the dipping sodium silicate solution concentration is
0.5-0.8mol/L。
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