CN108246361A - A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material - Google Patents
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material Download PDFInfo
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- CN108246361A CN108246361A CN201810014284.8A CN201810014284A CN108246361A CN 108246361 A CN108246361 A CN 108246361A CN 201810014284 A CN201810014284 A CN 201810014284A CN 108246361 A CN108246361 A CN 108246361A
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- cerium oxide
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- 239000000463 material Substances 0.000 title claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 27
- GZRQIDVFTAQASP-UHFFFAOYSA-N [Ce+3].[O-2].[Ti+4] Chemical compound [Ce+3].[O-2].[Ti+4] GZRQIDVFTAQASP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 26
- 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 abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000019441 ethanol Nutrition 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 8
- 238000009434 installation Methods 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 8
- 235000020679 tap water Nutrition 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- MBZLJHHVUVLDSX-UHFFFAOYSA-N cerium hydrochloride Chemical compound Cl.[Ce] MBZLJHHVUVLDSX-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
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002178 crystalline material Substances 0.000 abstract 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 abstract 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01D53/007—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 by irradiation
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- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
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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
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- 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
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material, including following processing steps：Cerous nitrate hydrochloric acid solution is prepared, six nitric hydrate ceriums are dissolved in hydrochloric acid solution and alcohol mixeding liquid；Titanium alcoholic solution is prepared, is heated to reflux being made with ethyl alcohol, methanol, isopropyl titanate, dodecyl trimethyl ammonium chloride, 25% methanol solution of tetraethyl ammonium hydroxide mass concentration；Hydrolytic polymerization mixes cerous nitrate hydrochloric acid solution and titanium alcoholic solution, and adjusts pH with sodium carbonate liquor；Pore-forming is crystallized, porous crystalline material is synthesized in the stainless steel cauldron of set temperature and pressure, molecular sieve type titanium cerium oxide catalysis material is made in filtered drying.Basic material using titanium cerium oxide to form skeleton, pore size is in micropore to macropore range, available for Adsorption of Organic removing in environment and light catalytic purifying process.
Description
Technical field
The invention belongs to environmental purification function Material Fields, and in particular to a kind of molecular sieve type titanium cerium oxide light for preparing is urged
Change the method for material.
Background technology
Photocatalysis pollution purification techniques passes through the research and development of nearly half a century, is gradually controlled in the pollution of various scales
Reason field has played increasing effect.The key factor of this technical field is the catalysis material of high activity.Organic dirt
Dye object is present in a variety of media such as big gas and water and solid waste.Organic pollution has due to molecular composition and structure difference
Different sizes, pore structure and size to catalysis material have different requirements.Although Photocatalytic Oxidation occurs
In the surface of material, and there must be the excitation process of specific light source, the adsorption capacity of porous material still lives to its photocatalysis
Property have important influence.Molecular sieve refers to there is uniform pore structure, can accommodate a kind of substance of organic molecule.Point
Son sieve is typically the alumino-silicate of crystal type, it is also possible to other element portions substitution framework silicons or aluminium, and form heteroatom type point
Son sieve.There are duct and cavity in framework of molecular sieve structure, so as to be a kind of high-efficiency adsorbent with very big specific surface area.
Molecular sieve containing titanium not only has stronger adsorption capacity, also has the work for declining organic pollution in solution environment in illumination condition
Property.Ce elements are added in titanium molecular sieve skeleton, so as to form binary composite oxides composition, photocatalytic activity can be improved.
Invention content
In view of the problems of the existing technology, the present invention is intended to provide a kind of prepare molecular sieve type titanium cerium oxide photocatalysis
The method of material.Basic material of such molecular sieve using titanium cerium oxide to form skeleton, pore size is in micropore to mesoporous model
It encloses, available for Adsorption of Organic removing in environment and light catalytic purifying process.
The technical solution adopted by the present invention is：
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material, including following processing steps：
Step 1：Prepare cerous nitrate hydrochloric acid solution
1.1 take 1,100 mL beakers, 22 ~ 27 mL 0.5mol/L hydrochloric acid solutions and 35 ~ 40 mL ethyl alcohol are added in, using magnetic force
Blender stirs evenly；
1.2 add in 4.3 ~ 4.8g, six nitric hydrate ceriums into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, nitre is made
Sour cerium hydrochloric acid solution, it is spare.
Step 2：Prepare titanium alcoholic solution
2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask
Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；
2.2 add in 170 ~ 210 mL ethyl alcohol, 53 ~ 66 mL methanol, 15 ~ 18 mL isopropyl titanates, 3 ~ 7 g 12 in flask
Alkyl trimethyl ammonium chloride, 12 ~ 16 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature are 78 DEG C, are returned
150 min are flowed, titanium alcoholic solution is made.
Step 3：Hydrolytic polymerization
3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78
DEG C, flow back 100 min；
3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix
The suspension of conjunction.
Step 4：Crystallize pore-forming
4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle
235 ~ 265 DEG C, 3 ~ 6 MPa of pressure, 76 ~ 98 h are reacted, then natural cooling；
4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；
4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product
Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material.
Preferably, the stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
Compared with prior art, the advantage of the invention is that：
The key technology of the present invention is that reasonably optimizing, accurate control synthesis item are carried out to materials synthesis processing step and raw material composition
Part, especially hydrolytic polymerization and crystallization pore forming process.Accuracy controlling can be carried out to the formation of titanium cerium oxide, ensure that monomer is former
Expect the controllable growth and polymerization process of ingredient, and generate the adjustable molecular sieve type materials of pore size.System provided by the invention
Standby process controllability is good, and product formation speed is fast, and properties of product are stablized, the powdery product particle size uniformity of generation, performance
Stablize.
Specific embodiment：
Embodiment 1
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material, including following processing steps：
Step 1：Prepare cerous nitrate hydrochloric acid solution
1.1 take 1,100 mL beakers, 22 mL 0.5mol/L hydrochloric acid solutions and 35 mL ethyl alcohol are added in, using magnetic stirring apparatus
It stirs evenly；
1.2 add in six nitric hydrate ceriums of 4.3g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made
Hydrochloric acid solution, it is spare.
Step 2：Prepare titanium alcoholic solution
2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask
Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；
2.2 add in 170 mL ethyl alcohol, 53 mL methanol, 15 mL isopropyl titanates, 3 g trimethyl chlorine in flask
Change ammonium, 12 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made
Alcoholic solution.
Step 3：Hydrolytic polymerization
3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78
DEG C, flow back 100 min；
3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix
The suspension of conjunction.
Step 4：Crystallize pore-forming
4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle
235 DEG C, 3 MPa of pressure, 76 h are reacted, then natural cooling；
4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；
4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product
Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material.
The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
Embodiment 2
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material, including following processing steps：
Step 1：Prepare cerous nitrate hydrochloric acid solution
1.1 take 1,100 mL beakers, 25 mL 0.5mol/L hydrochloric acid solutions and 37 mL ethyl alcohol are added in, using magnetic stirring apparatus
It stirs evenly；
1.2 add in six nitric hydrate ceriums of 4.6g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made
Hydrochloric acid solution, it is spare.
Step 2：Prepare titanium alcoholic solution
2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask
Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；
2.2 add in 190 mL ethyl alcohol, 59 mL methanol, 16 mL isopropyl titanates, 5 g trimethyl chlorine in flask
Change ammonium, 14 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made
Alcoholic solution.
Step 3：Hydrolytic polymerization
3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78
DEG C, flow back 100 min；
3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix
The suspension of conjunction.
Step 4：Crystallize pore-forming
4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle
253 DEG C, 4.5 MPa of pressure, 83 h are reacted, then natural cooling；
4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；
4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product
Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material.
The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
Embodiment 3
A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material, including following processing steps：
Step 1：Prepare cerous nitrate hydrochloric acid solution
1.1 take 1,100 mL beakers, 27 mL 0.5mol/L hydrochloric acid solutions and 40 mL ethyl alcohol are added in, using magnetic stirring apparatus
It stirs evenly；
1.2 add in six nitric hydrate ceriums of 4.8g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made
Hydrochloric acid solution, it is spare.
Step 2：Prepare titanium alcoholic solution
2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask
Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；
2.2 add in 210 mL ethyl alcohol, 66 mL methanol, 18 mL isopropyl titanates, 7 g trimethyl chlorine in flask
Change ammonium, 16 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made
Alcoholic solution.
Step 3：Hydrolytic polymerization
3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78
DEG C, flow back 100 min；
3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix
The suspension of conjunction.
Step 4：Crystallize pore-forming
4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle
265 DEG C, 6 MPa of pressure, 98 h are reacted, then natural cooling；
4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；
4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product
Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material.
The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
Claims (5)
- A kind of 1. method for preparing molecular sieve type titanium cerium oxide catalysis material, which is characterized in that including following processing steps：Step 1：Prepare cerous nitrate hydrochloric acid solution1.1 take 1,100 mL beakers, 22 ~ 27 mL 0.5mol/L hydrochloric acid solutions and 35 ~ 40 mL ethyl alcohol are added in, using magnetic force Blender stirs evenly；1.2 add in 4.3 ~ 4.8g, six nitric hydrate ceriums into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, nitre is made Sour cerium hydrochloric acid solution, it is spare；Step 2：Prepare titanium alcoholic solution2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；2.2 add in 170 ~ 210 mL ethyl alcohol, 53 ~ 66 mL methanol, 15 ~ 18 mL isopropyl titanates, 3 ~ 7 g 12 in flask Alkyl trimethyl ammonium chloride, 12 ~ 16 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature are 78 DEG C, are returned 150 min are flowed, titanium alcoholic solution is made；Step 3：Hydrolytic polymerization3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78 DEG C, flow back 100 min；3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix The suspension of conjunction；Step 4：Crystallize pore-forming4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle 235 ~ 265 DEG C, 3 ~ 6 MPa of pressure, 76 ~ 98 h are reacted, then natural cooling；4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material.
- 2. a kind of method for preparing molecular sieve type titanium cerium oxide catalysis material as described in claim 1, it is characterised in that：The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
- 3. a kind of method for preparing molecular sieve type titanium cerium oxide catalysis material as described in claim 1, which is characterized in that Including following processing steps：Step 1：Prepare cerous nitrate hydrochloric acid solution1.1 take 1,100 mL beakers, 22 mL 0.5mol/L hydrochloric acid solutions and 35 mL ethyl alcohol are added in, using magnetic stirring apparatus It stirs evenly；1.2 add in six nitric hydrate ceriums of 4.3g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made Hydrochloric acid solution, it is spare；Step 2：Prepare titanium alcoholic solution2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；2.2 add in 170 mL ethyl alcohol, 53 mL methanol, 15 mL isopropyl titanates, 3 g trimethyl chlorine in flask Change ammonium, 12 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made Alcoholic solution；Step 3：Hydrolytic polymerization3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78 DEG C, flow back 100 min；3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix The suspension of conjunction；Step 4：Crystallize pore-forming4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle 235 DEG C, 3 MPa of pressure, 76 h are reacted, then natural cooling；4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material；The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
- 4. a kind of method for preparing molecular sieve type titanium cerium oxide catalysis material as described in claim 1, which is characterized in that Including following processing steps：Step 1：Prepare cerous nitrate hydrochloric acid solution1.1 take 1,100 mL beakers, 25 mL 0.5mol/L hydrochloric acid solutions and 37 mL ethyl alcohol are added in, using magnetic stirring apparatus It stirs evenly；1.2 add in six nitric hydrate ceriums of 4.6g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made Hydrochloric acid solution, it is spare；Step 2：Prepare titanium alcoholic solution2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；2.2 add in 190 mL ethyl alcohol, 59 mL methanol, 16 mL isopropyl titanates, 5 g trimethyl chlorine in flask Change ammonium, 14 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made Alcoholic solution；Step 3：Hydrolytic polymerization3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78 DEG C, flow back 100 min；3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix The suspension of conjunction；Step 4：Crystallize pore-forming4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle 253 DEG C, 4.5 MPa of pressure, 83 h are reacted, then natural cooling；4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material；The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
- 5. a kind of method for preparing molecular sieve type titanium cerium oxide catalysis material as described in claim 1, which is characterized in that Including following processing steps：Step 1：Prepare cerous nitrate hydrochloric acid solution1.1 take 1,100 mL beakers, 27 mL 0.5mol/L hydrochloric acid solutions and 40 mL ethyl alcohol are added in, using magnetic stirring apparatus It stirs evenly；1.2 add in six nitric hydrate ceriums of 4.8g into beaker, are stirred on magnetic stirring apparatus to being completely dissolved, cerous nitrate is made Hydrochloric acid solution, it is spare；Step 2：Prepare titanium alcoholic solution2.1 take two mouthfuls of 500 mL boiling flasks 1, are placed in thermostat water bath, and installation is surveyed respectively on two interfaces of flask Galvanic couple and spherical condensation tube are warmed, using tap water as cooling agent in condenser pipe；2.2 add in 210 mL ethyl alcohol, 66 mL methanol, 18 mL isopropyl titanates, 7 g trimethyl chlorine in flask Change ammonium, 16 mL tetraethyl ammonium hydroxides mass concentration, 25% methanol solution, solution temperature is 78 DEG C, and flow back 150 min, and titanium is made Alcoholic solution；Step 3：Hydrolytic polymerization3.1 pour into cerous nitrate hydrochloric acid solution made from step 1.2 in the flask for holding titanium alcoholic solution, keep solution temperature 78 DEG C, flow back 100 min；3.2 are slowly added to 2 mol/L sodium carbonate liquors into flask, until the pH of solution reaches 7.0, obtain solid-liquid and mix The suspension of conjunction；Step 4：Crystallize pore-forming4.1 pour into suspension made from step 3.2 in stainless steel cauldron, and reaction kettle is closed, keep temperature in reaction kettle 265 DEG C, 6 MPa of pressure, 98 h are reacted, then natural cooling；4.2 filter products therefrom by filter paper, and filter cake is cleaned with deionized water；4.3 are placed in filter cake in constant temperature electric heating drying box, in 230 DEG C of dry 48 h, are fully ground in porcelain mortar, make product Grain size is less than 5 μm, obtains molecular sieve type titanium cerium oxide catalysis material；The stir speed (S.S.) of the magnetic stirring apparatus is 200 rpm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993374A (en) * | 2018-07-25 | 2018-12-14 | 沈阳理工大学 | A kind of preparation method of one-dimensional mesoporous catalysis material |
| CN109399726A (en) * | 2018-11-15 | 2019-03-01 | 沈阳理工大学 | A kind of preparation method of iron lanthanum-oxides molecular sieve type scavenging material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302441A (en) * | 1999-04-12 | 2000-10-31 | Jsr Corp | Titanium dioxide precursor composition and titanium dioxide |
| CN105797707A (en) * | 2016-04-14 | 2016-07-27 | 沈阳理工大学 | Method for preparing mesoporous titanic acid lanthanum zinc photocatalyst |
| CN105883845A (en) * | 2016-04-14 | 2016-08-24 | 沈阳理工大学 | Method for preparing molecular sieve with Ti-Ai oxide as framework |
| CN106186052A (en) * | 2016-07-21 | 2016-12-07 | 沈阳理工大学 | A kind of preparation method of macropore hollow Cerium titanate microsphere |
| CN106495178A (en) * | 2016-09-19 | 2017-03-15 | 沈阳理工大学 | A kind of method for preparing mesoporous molecular sieve metatitanic acid neodymium surrounding purifying material |
| CN107308983A (en) * | 2017-06-30 | 2017-11-03 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature is except interior VOC catalyst and preparation method thereof |
-
2018
- 2018-01-08 CN CN201810014284.8A patent/CN108246361B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302441A (en) * | 1999-04-12 | 2000-10-31 | Jsr Corp | Titanium dioxide precursor composition and titanium dioxide |
| CN105797707A (en) * | 2016-04-14 | 2016-07-27 | 沈阳理工大学 | Method for preparing mesoporous titanic acid lanthanum zinc photocatalyst |
| CN105883845A (en) * | 2016-04-14 | 2016-08-24 | 沈阳理工大学 | Method for preparing molecular sieve with Ti-Ai oxide as framework |
| CN106186052A (en) * | 2016-07-21 | 2016-12-07 | 沈阳理工大学 | A kind of preparation method of macropore hollow Cerium titanate microsphere |
| CN106495178A (en) * | 2016-09-19 | 2017-03-15 | 沈阳理工大学 | A kind of method for preparing mesoporous molecular sieve metatitanic acid neodymium surrounding purifying material |
| CN107308983A (en) * | 2017-06-30 | 2017-11-03 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature is except interior VOC catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| DOINA LUTIC等: ""Mesoporous cerium-doped titania for the photocatalytic removal ofpersistent dyes"", 《CATALYSIS TODAY》 * |
| JIANGRONG XIAO等: ""Preparation, phase transformation and photocatalytic activities of cerium-doped mesoporous titania nanoparticles"", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| 丁士文等: ""纳米CeO2-TiO2复合介孔材料的制备与性能"", 《纳米科技》 * |
| 李旭光等: ""不同硅铝比的Beta/ MCM-41复合分子筛的合成和性能"", 《复旦学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993374A (en) * | 2018-07-25 | 2018-12-14 | 沈阳理工大学 | A kind of preparation method of one-dimensional mesoporous catalysis material |
| CN108993374B (en) * | 2018-07-25 | 2020-12-15 | 沈阳理工大学 | Preparation method of one-dimensional mesoporous photocatalytic material |
| CN109399726A (en) * | 2018-11-15 | 2019-03-01 | 沈阳理工大学 | A kind of preparation method of iron lanthanum-oxides molecular sieve type scavenging material |
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