CN109529917A - TiO2, the preparation method of CuO/ZSM-5 molecular sieve catalyst - Google Patents
TiO2, the preparation method of CuO/ZSM-5 molecular sieve catalyst Download PDFInfo
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- 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
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- 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
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- B01D53/8603—Removing sulfur compounds
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses TiO2, the preparation method of CuO/ZSM-5 molecular sieve catalyst, by ultrasonic oscillation, magnetization, oil bath heating waits the catalyst of modified methods synthetic sweetening denitration, and the catalyst desulfurizing effect prepared is good.
Description
The application is the divisional application of following application: the applying date is on November 03rd, 2016, application No. is
201610955961.7, the preparation method of a kind of entitled CuO, TiO2 modified desulphurization catalyst.
Technical field
The present invention relates to TiO2, the preparation method of CuO/ZSM-5 molecular sieve catalyst belongs to technical field of desulfurization.
Background technique
Important petroleum resources are needed to carry out deep processing, wherein fluid catalytic cracking (FCC) is essential
Process.However often with the part nitrogen being present in feedstock oil in the regenerated flue gas of FCC, and it is drained into the form of NOx
In atmosphere, be discharged together there are also SO2.A large amount of discharges of NOx and SO2 will cause serious environmental pollution, especially be formed
Acid rain can not only damage the ecosystem, but also will affect the health and normal life of the mankind.The study found that
The female equal researchs hair of photochemistry cigarette Guo's tin for generating destruction ozone layer is reacted in NOx meeting with volatile organic matter under the action of light and heat
It is existing, using 3mol/LH2SO4 solution treated HZSM-5 as carrier, load the Cu/HZSM-5 catalyst of 4%Cu (mass fraction)
Denitration activity highest；Li Zhe etc. (2006；2008) unstability of oxygen, vapor is carried out for Fe-ZSM-5 catalyst
Fe/ZSM-5 catalyst decomposes the research of NO activity and rare earth element promotor action but at present to the support type of simultaneous SO_2 and NO removal
The research report of catalyst is seldom.Methane is under conditions of reducing agent, there are also infusion processes to combine preparation difference using directly addition
The TiO2 of the CuO:TiO2 of mass ratio, CuO/ZSM-5 molecular sieve catalyst inquire into the best optimum load of desulphurization denitration activity
Amount, to provide a kind of reference for industrial development desulphurization denitration catalyst.
Summary of the invention
To achieve the goals above, the technical solution adopted by the present invention is that: TiO2, CuO/ZSM-5 molecular sieve catalyst
Preparation method, comprising the following steps:
Step 1, first by copper oxide, titanium dioxide, sodium hydroxide, dehydrated alcohol 80 DEG C of oil baths under ultrasonic oscillation are super
Sound 3h removal of impurities；
Step 2, by tetraethyl orthosilicate, aluminium isopropoxide, deionized water, liquid template agent morpholine, tetraethyl hydroxide
Ammonium is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and deionized water, dehydrated alcohol, with per minute 20 is then added dropwise
It drips speed to be added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Step 5 dissolves copper oxide in deionized water, and then oxidation copper liquor is added in above-mentioned solution,
Coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Step 9 dissolves titanium dioxide in deionized water, and by infusion process, CuO/ZSM-5 molecular sieve obtained is urged
Agent is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotary evaporation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in device, and obtained catalyst precursor is dry at 110 DEG C in electric drying oven with forced convection
2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
The invention has the advantages that: TiO2, CuO/ZSM-5 molecular sieve catalyst has relatively high desulphurization denitration rate, this hair
It is bright that by introducing, TiO2, CuO, during the preparation process by magnetic agitation, crystallization under nitrogen atmosphere is calcined under sufficient air, this
A little method of modifying make catalyst effect obtained greatly promote and greatly improve desulphurization denitration rate, TiO2, CuO mass
Than for 1:3,10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml gone
Ionized water, 5ml morpholine, TiO2 obtained under 5ml tetraethyl ammonium hydroxide, CuO/ZSM-5 molecular sieve catalyst desulphurization denitration
Effect is best.
Specific embodiment
Embodiment 1
TiO2 is prepared, CuO mass ratio is the sample of 1:1.2gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 2
TiO2 is prepared, CuO mass ratio is the sample of 1:2.2gTiO2,4gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 4g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 3
TiO2 is prepared, CuO mass ratio is the sample of 1:3.2gTiO2,6gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 6g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 4
TiO2 is prepared, CuO mass ratio is the sample of 1:4.2gTiO2,8gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 8g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3,50ml deionized water is then added dropwise, dehydrated alcohol is molten, with every
Minute 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 5
TiO2 is prepared, CuO mass ratio is the sample of 1:5.10gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 10g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is super
The lower 80 DEG C of oil bath ultrasound 3h removal of impurities of sound wave shock；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added in flask by step 3, and 50ml deionized water is then added dropwise, and dehydrated alcohol dissolves, with
20 drop speed per minute is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 6
TiO2 is prepared, CuO mass ratio is the sample of 2:1.4gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 4g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 7
TiO2 is prepared, CuO mass ratio is the sample of 3:1.6gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 6g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added in flask by step 3, and 50ml deionized water is then added dropwise, and dehydrated alcohol dissolves, with
20 drop speed per minute is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 8
TiO2 is prepared, CuO mass ratio is the sample of 4:1.8gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 8g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added in flask by step 3, and 50ml deionized water is then added dropwise, and dehydrated alcohol dissolves, with
20 drop speed per minute is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Embodiment 9
TiO2 is prepared, CuO mass ratio is the sample of 5:1.10gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 10g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is super
The lower 80 DEG C of oil bath ultrasound 3h removal of impurities of sound wave shock；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3,50ml deionized water is then added dropwise, dehydrated alcohol is molten, with every
Minute 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Reference examples 1
The preparation sample that only addition TiO2 is modified.6gTiO2,10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol, the positive silicon of 8ml
Sour tetra-ethyl ester, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 6g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is under ultrasonic oscillation
80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3,50ml deionized water is then added dropwise, dehydrated alcohol is molten, with every
Minute 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating into coagulant liquid；
Step 5, by coagulant liquid aging 12h in air；
Step 6 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 7 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, ZSM-5 molecular sieve catalyst is obtained；
Titanium dioxide is dissolved in 50ml deionized water by step 8, and by infusion process, ZSM-5 molecular sieve obtained is urged
Agent is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotary evaporation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in device, and obtained catalyst precursor is dry at 110 DEG C in electric drying oven with forced convection
2h；
Step 9 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2/ZSM-5 molecular sieve catalyst；
Step 10, by TiO2/ZSM-5 molecular sieve catalyst obtained under sampling machine sample preparation at 40-60 mesh.
Reference examples 2
The sample of CuO is only added in preparation.6gCuO, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol, the positive silicic acid tetrem of 8ml
Ester, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is 80 under ultrasonic oscillation
DEG C oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3,50ml deionized water is then added dropwise, dehydrated alcohol is molten, with every
Minute 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained；
Step 9 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve catalytic
Agent；
Step 10, by CuO/ZSM-5 molecular sieve catalyst obtained under sampling machine sample preparation at 40-60 mesh.
Reference examples 3
TiO2 is prepared, CuO mass ratio is the sample of 1:3.2gTiO2,6gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 6g copper oxide, 2g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and stirs oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while being stirred 80 DEG C of 2h of oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in stirring 90 DEG C of 3h of oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, crystallization 12h under nitrogen atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in stirring 90 DEG C of 3h of oil bath heating in titanium dioxide aqueous solution and is put into rotary evaporation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in device, and obtained catalyst precursor is dry at 110 DEG C in electric drying oven with forced convection
2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
Reference examples 4
TiO2 is prepared, CuO mass ratio is the sample of 3:1.6gTiO2,2gCuO, 10ml2mol/L sodium hydroxide, 30ml are anhydrous
Ethyl alcohol, 8ml tetraethyl orthosilicate, the aluminium isopropoxide of 9g, 200ml deionized water, 5ml morpholine, 5ml tetraethyl ammonium hydroxide.
Step 1, first by 2g copper oxide, 6g titanium dioxide, 10ml2mol/L sodium hydroxide, 30ml dehydrated alcohol is in ultrasound
Wave shakes lower 80 DEG C of oil bath ultrasound 3h removal of impurities；
Step 2, by 8ml tetraethyl orthosilicate, 9g aluminium isopropoxide, 50ml deionized water, 5ml liquid template agent morpholine,
5ml tetraethyl ammonium hydroxide is in 50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and 50ml deionized water, dehydrated alcohol, with every point is then added dropwise
Clock 20 drips speed and is added dropwise, and magnetic agitation oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, and template morpholine, tetraethyl ammonium hydroxide then is being added dropwise
It is added dropwise with 30 drop speed per minute, is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Copper oxide is dissolved in 50ml ionized water by step 5, and oxidation copper liquor is then added to above-mentioned solution
In, coagulant liquid is made in 90 DEG C of 3h of magnetic agitation oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter, then by reaction kettle
It is put into the speed in microwave reactor with 15kap/min and boosts to 200kpa, temperature rises to 150 with the speed of 10 DEG C/min
DEG C, the crystallization 12h under air atmosphere；
Then step 8 is centrifugated under centrifugal separator, dry, is finally forged under sufficient air atmosphere in Muffle furnace
6h is burnt, CuO/ZSM-5 molecular sieve catalyst is obtained
Titanium dioxide is dissolved in 50ml deionized water by step 9, by infusion process, by CuO/ZSM-5 molecule obtained
Sieve catalyst is immersed in 90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution and is put into rotation after standing for 24 hours in air
Vacuum is rotated to moisture and is evaporated at 80 DEG C in evaporator, and obtained catalyst precursor is in electric drying oven with forced convection at 110 DEG C
Dry 2h；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve is urged
Agent；
Step 11, by TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
The activity rating of molecular sieve catalyst
On atmospheric fixed bed flow method micro-reaction equipment, the activity that catalyst reacts CH4+NO+SO2 has been investigated.
Automatic temperature control instrument controls temperature-programmed reaction, and 0~500 DEG C of heating rate is 10 DEG C/min, stablizes at 500 DEG C.Reaction gas
Group becomes (volume fraction): 0.05% NO, 0.1% SO2,0.15% CH4, N2 are carrier gas.Catalyst loading 400mg
(40~60 mesh), gas flow 100mL/min, quartz glass reaction bore Φ=6mm. reaction product comprehensive cigarette of KM9106
Gas analyzer, nitrogen-oxide analyzer, and mass spectroscopy calculate conversion ratio according to the amount of residue NO and SO2 in product,
Desulphurization denitration rate at one 500 DEG C of table
| Sample | Desulfurization degree % | Denitration % |
| Embodiment 1 | 45.2 | 58 |
| Embodiment 2 | 53.4 | 68.2 |
| Embodiment 3 | 94.3 | 97.2 |
| Embodiment 4 | 65.5 | 67.7 |
| Embodiment 5 | 43.3 | 48.5 |
| Embodiment 6 | 55.6 | 60.1 |
| Embodiment 7 | 92.2 | 95.4 |
| Embodiment 8 | 68.4 | 71.5 |
| Embodiment 9 | 45.4 | 59.2 |
| Reference examples 1 | 32.1 | 20.2 |
| Reference examples 2 | 35.8 | 23.1 |
| Reference examples 3 | 40.1 | 48.7 |
| Reference examples 4 | 36.2 | 38.4 |
The result shows that embodiment 3 is best there are also 7 desulfurization off sulfide effect of embodiment, TiO2, the synergistic effect of CuO reach at this time
It is best.It can be found that comparative example 1,2,3,4,5, when various operations are identical, TiO2 when CuO mass ratio is 1: 3, makes
The TiO2 obtained, CuO/ZSM-5 molecular sieve catalyst catalytic effect is preferably that desulphurization denitration rate is high, obtained under other ratios
TiO2, CuO/ZSM-5 molecular sieve catalyst, the synergistic action effect between TiO2, CuO are not fine.Implementation column 1,6 is compared,
7,8,9, it can be found that TiO2 obtained when TiO2, CuO mass ratio are 3: 1, CuO/ZSM-5 molecular sieve catalyst catalytic effect is most
Good, increase or reduction TiO2 with titanium dioxide, the synergistic effect of CuO, which can all decline catalytic effect, can all reduce.It is real
Column 3 and comparative example 1 are applied, embodiment 7 is compared with comparative example 2 it can be found that obtaining single copper oxide or titanium dioxide is only added
CuO/ZSM-5 molecular sieve catalyst, TiO2/ZSM-5 molecular sieve catalyst and two kinds of TiO2 are added, made from CuO
TiO2, CuO/ZSM-5 molecular sieve catalyst are compared to TiO2 has been lacked, and CuO synergistic effect is so disengaging denitration effect is bad, especially
It is that maximum is influenced on denitration.Implementation column 3 is compared, reference examples 3 are it can be found that the TiO2 made from magnetic agitation, CuO/ZSM-5 point
Sub- sieve catalyst desulfurization off sulfide effect is obtained under magnetic stirring significantly better than not.Comparative example 7, reference examples 4 are found
TiO2 made from microwave reaction crystallization under nitrogen atmosphere, CuO/ZSM-5 molecular sieve catalyst desulfurization off sulfide effect are better than
TiO2 obtained under air atmosphere, CuO/ZSM-5 molecular sieve catalyst.
Claims (3)
1.TiO2, the preparation method of CuO/ZSM-5 molecular sieve catalyst, it is characterised in that: pass through ultrasonic oscillation, magnetization, oil bath
Heating, waits the catalyst of modified methods synthetic sweetening denitration, specific preparation step includes:
Step 1, first by copper oxide, titanium dioxide, sodium hydroxide, dehydrated alcohol 80 DEG C of oil bath ultrasound 3h under ultrasonic oscillation
Removal of impurities；
Step 2, by tetraethyl orthosilicate, aluminium isopropoxide, deionized water, liquid template agent morpholine, tetraethyl ammonium hydroxide exists
50 DEG C of 2h removal of impurities of ultrasonic oscillation water-bath；
Tetraethyl orthosilicate is added drop-wise in flask by step 3, and deionized water, dehydrated alcohol, with 20 drop speed per minute is then added dropwise
Degree is added dropwise, and stirs oil bath heating 3h simultaneously；
Aluminium isopropoxide is added in above-mentioned solution by step 4, template morpholine then is being added dropwise, tetraethyl ammonium hydroxide is with every
Minute 30 drips speed and is added dropwise, and is being added dropwise while carrying out 80 DEG C of 2h of magnetic agitation oil bath heating；
Step 5 dissolves copper oxide in deionized water, then oxidation copper liquor is added in above-mentioned solution, in magnetic force
Coagulant liquid is made in stirring 90 DEG C of 3h of oil bath heating；
Step 6, by coagulant liquid aging 12h in air；
Step 7 pours into coagulant liquid in the reaction kettle that polytetrafluoroethylene (PTFE) is liner by flow diverter；
Then step 8 is centrifugated under centrifugal separator, dry, finally calcines 6h under sufficient air atmosphere in Muffle furnace,
Obtain CuO/ZSM-5 molecular sieve catalyst；
Step 9 dissolves titanium dioxide in deionized water, by infusion process, by CuO/ZSM-5 molecular sieve catalyst obtained
90 DEG C of 3h of magnetic agitation oil bath heating in titanium dioxide aqueous solution are immersed in be put into rotary evaporator after standing for 24 hours in air
Vacuum, which is rotated to moisture, at 80 DEG C is evaporated, and obtained catalyst precursor dries 2h in electric drying oven with forced convection at 110 DEG C；
Step 10 finally calcines 8h under sufficient air atmosphere in Muffle furnace, obtains TiO2, CuO/ZSM-5 molecular sieve catalyst；
Step 11, by TiO obtained2, CuO/ZSM-5 molecular sieve catalyst under sampling machine sample preparation at 40-60 mesh.
2. TiO according to claim 12, the preparation method of CuO/ZSM-5 molecular sieve catalyst, which is characterized in that described
Step 2 be magnetic agitation oil bath heating 3h.
3. TiO according to claim 12, the preparation method of CuO/ZSM-5 molecular sieve catalyst, which is characterized in that described
Step 7 in, specifically include: by coagulant liquid by flow diverter pour into polytetrafluoroethylene (PTFE) be liner reaction kettle in, then will be anti-
The speed for answering kettle to be put into microwave reactor with 15kap/min boosts to 200kpa, and temperature is risen to the speed of 10 DEG C/min
150 DEG C, crystallization 12h under nitrogen atmosphere.
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