CN106378122A - Silica gel loaded titanium catalyst, preparation method and application thereof - Google Patents
Silica gel loaded titanium catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN106378122A CN106378122A CN201610735457.6A CN201610735457A CN106378122A CN 106378122 A CN106378122 A CN 106378122A CN 201610735457 A CN201610735457 A CN 201610735457A CN 106378122 A CN106378122 A CN 106378122A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- titanium catalyst
- unformed
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000741 silica gel Substances 0.000 title claims abstract description 77
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 51
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000010926 purge Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 26
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 22
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000001294 propane Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910003849 O-Si Inorganic materials 0.000 abstract description 3
- 229910003872 O—Si Inorganic materials 0.000 abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000012229 microporous material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 4
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- GPKFMIVTEHMOBH-UHFFFAOYSA-N cumene;hydrate Chemical compound O.CC(C)C1=CC=CC=C1 GPKFMIVTEHMOBH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 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 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silica gel loaded titanium catalyst, a preparation method and application thereof. The preparation method of the silica gel loaded titanium catalyst includes: (1) moulding amorphous silica gel powder into amorphous silica gel particles; (2) heating the amorphous silica particles to 200-500DEG C, and conducting purging under N2 to remove moisture; heating liquid TiCl4, fully mixing the gasified TiCl4 with nitrogen, then introducing the mixture into a chemical vapor deposition device, raising the temperature to 600-1000DEG C, and carrying out reaction; performing cooling, conducting N2 purging, and carrying out cooling to room temperature; and (3) conducting roasting to obtain the silica gel loaded titanium catalyst. The silica gel loaded titanium catalyst breaks the pore size limitation of microporous materials, and increases TiO2 dispersity, most active components are exposed to the catalyst surface, and the formation of the Ti-O-Si bond also plays a stabilization role to anatase TiO2. The catalyst can be used for catalyzing selective oxidation of propylene to achieve one-step preparation of propylene oxide, and the catalytic activity of epoxidation reaction and the selectivity of propylene oxide are both improved.
Description
Technical field
The present invention relates to a kind of silica gel load titanium catalyst and preparation method.
Background technology
Shell chemical company develops TiO earliest2-SiO2Material, the specific surface area of unformed silicon materials used and aperture
Less be oxidized to the catalyst of propylene oxide reaction as Propylene Selectivity so that the load capacity very little of titanium, have impact on catalysis effect
Really.
United States Patent (USP) US4410501 discloses the synthetic method of TS-1 molecular sieve, and this molecular sieve component is TiO2-SiO2, its
Pore size only has 0.55nm it is difficult to be catalyzed the selective oxidation reaction that macromole organic peroxide participates in.
It is template that TanevPT etc. adopts n-dodecylamine, and isopropyl titanate and tetraethyl orthosilicate are raw material, ethanol and isopropyl
Alcohol-water solution is solvent, and room temperature condition synthesizes TiO2-SiO2Material.But the titanium synthesized by hydrothermal method is mainly with the shape of four-coordination
Formula is embedded in body phase, have impact on catalytic effect.
Silica gel loading titanium (TiO2-SiO2) catalyst can be used for the selective oxidation reaction of catalyzed alkene, it is alternatively arranged as light and urge
The catalyst of change, ester exchange and isomerization reaction.TiO2There are anatase, rutile and three kinds of crystalline structures of brockite, from
The specific surface area of body is little and duct is little.Wherein Detitanium-ore-type TiO2There is good activity, but unstable at high temperature, easily
It is converted into inert rutile structure, loses catalysis activity, limit its industrialization development.Research shows, TiO2-SiO2Load oxygen
The Ti-O-Si key being formed between compound is to Detitanium-ore-type TiO2Serve Stabilization.
As noted previously, as the restriction of duct size, the catalysis macromole participation that micropore Si catalyst can not be good
Epoxidation reaction.The active component of the mesoporous catalyst of hydrothermal method synthesis is embedded in catalytic inner again mostly.Therefore, find
A kind of suitable preparation method, develops new catalyst, improves catalyst aperture and titanium load capacity, makes active component most of
Be exposed to catalyst surface, and so that Detitanium-ore-type is tended towards stability, so improve activity and the selectivity of propylene ring oxidation reaction with
And Catalyst Production efficiency, have very important significance.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides with cheap inorganic titanium compound as titanium source, unformed
The aperture that silica gel is prepared for carrier is big, thermally-stabilised good, there is the good a kind of silica gel loading titanium of large specific surface area, catalytic performance
Catalyst.
Second object of the present invention is to provide preparation method simple, easily operated, a kind of high silica gel load of repeatability
The preparation method of titanium catalyst.
This 3rd bright purpose is to provide silica gel load titanium catalyst to aoxidize a step in catalysis Propylene Selectivity to prepare ring
The purposes of Ethylene Oxide.
Technical scheme is summarized as follows：
A kind of silica gel load titanium catalyst, is that the unformed silica gel particle of carrier is loaded with TiO2.
The preparation method of silica gel load titanium catalyst, comprises the steps：
(1) unformed silica gel powder is shaped to unformed silica gel particle；
(2) unformed silica gel particle is placed in chemical vapor deposition unit, is warming up to 200-500 DEG C, in 50-200ml/
The N of min2Protection is lower to purge at least 1h, removes moisture；By liquid TiCl4It is heated to 30～100 DEG C, fully mixed with nitrogen after gasification
It is passed through after conjunction in described chemical vapor deposition unit, TiCl4The flow of steam is (0.05-0.5) ml/min, and nitrogen flow is
50ml/min, is warming up to 600-1000 DEG C, reacts 1～3h；Chemical vapor deposition unit is cooled to 200-500 DEG C, 50-
The N of 200ml/min2Lower purging at least 2h, is down to room temperature；
(3) under air atmosphere, 400-600 DEG C of roasting 4-6h be warming up to 5-15 DEG C/min, obtain silica gel loading titanium and urge
Agent.
Unformed silica gel powder is shaped to the step of unformed silica gel particle preferably：
By unformed rubber powder end and boehmite 60-90 in mass ratio:The ratio of 10-40 mixes in kneader must mix
Compound, adds the aqueous solution of nitric acid that mass concentration is 2%-10%, and the ratio of described mixture and described aqueous solution of nitric acid is
10g:5-10mL, stirring mixing, it is extruded into strip, 70-110 DEG C of drying 8-12h, under air conditionses, in 500-550 DEG C of roasting 3-
5h, grinds to form granule, crosses 30-40 mesh sieve, obtains unformed silica gel particle.
Above-mentioned silica gel load titanium catalyst aoxidizes the purposes that a step prepares expoxy propane (PO), bag in catalysis Propylene Selectivity
Include following steps：In fixed bed, in proportion, put into 0.5g silica gel load titanium catalyst, with propylene, cumyl hydroperoxide
(CHP) it is raw material, cumyl hydroperoxide is dissolved in isopropylbenzene, at 50-110 DEG C, reaction pressure is 0.1-8M Pa, empty
Speed controls in 1-10h-1, reaction 1-12h generation expoxy propane；The mol ratio of described cumyl hydroperoxide, propylene and isopropylbenzene
For 1:1-10:4-50, described silica gel load titanium catalyst is 1-5 with the mass ratio of cumyl hydroperoxide:10.
Advantages of the present invention：
The silica gel load titanium catalyst of present invention preparation has broken the limitation of poromerics pore size, increased TiO2
Dispersion, active component major part is exposed to catalyst surface, and the formation of Ti-O-Si key is also to Detitanium-ore-type TiO2Serve steady
It is set for using.Silica gel loading titanium catalyst Propylene Selectivity aoxidizes a step and prepares expoxy propane, improves epoxidation reaction
Catalysis activity and the selectivity of expoxy propane, provide prerequisite for accelerating industrialization paces.
Brief description
Fig. 1 is the XRD spectrum of silica gel load titanium catalyst.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated.
Embodiment 1
The method that unformed silica gel powder is shaped to unformed silica gel particle, comprises the steps：
By unformed silica gel powder (commodity) and boehmite in mass ratio 80:20 ratio mixes in kneader
Mixture, adds the aqueous solution of nitric acid that mass concentration is 5%, the ratio of described mixture and described aqueous solution of nitric acid is 10g:
8mL, stirring mixing, it is extruded into strip, 100 DEG C of drying 10h, under air conditionses, in 530 DEG C of roasting 4h, grind to form granule, cross 30-
40 mesh sieves, obtain unformed silica gel particle.
Embodiment 2
The method that unformed silica gel powder is shaped to unformed silica gel particle, comprises the steps：
By unformed silica gel powder and boehmite in mass ratio 60:40 ratio mixes in kneader and must mix
Thing, adds the aqueous solution of nitric acid that mass concentration is 10%, the ratio of described mixture and described aqueous solution of nitric acid is 10g:10mL,
Stirring mixing, is extruded into strip, 70 DEG C of drying 12h, under air conditionses, in 500 DEG C of roasting 5h, grinds to form granule, crosses 30-40 mesh
Sieve, obtains unformed silica gel particle.
Embodiment 3
The method that unformed silica gel powder is shaped to unformed silica gel particle, comprises the steps：
By unformed silica gel powder and boehmite in mass ratio 90:10 ratio mixes in kneader and must mix
Thing, adds the aqueous solution of nitric acid that mass concentration is 2%, the ratio of described mixture and described aqueous solution of nitric acid is 10g:5mL, stirs
Mix mixing, be extruded into strip, 110 DEG C of drying 8h, under air conditionses, in 550 DEG C of roasting 3h, grind to form granule, cross 30-40 mesh sieve,
Obtain unformed silica gel particle.
Embodiment 4
The preparation method of silica gel load titanium catalyst, comprises the steps：
(1) method of embodiment 1 prepares unformed silica gel particle；
(2) unformed silica gel particle is placed in chemical vapor deposition unit, is warming up to 350 DEG C, in the N of 100ml/min2
Protection is lower to purge 1h, removes moisture；By liquid TiCl4It is heated to 65 DEG C, after being sufficiently mixed with nitrogen after gasification, be passed through describedization
Learn in vapor phase growing apparatus, TiCl4The flow of steam is 0.1ml/min, and nitrogen flow is 50ml/min, is warming up to 800 DEG C, instead
Answer 2h；Chemical vapor deposition unit is cooled to 350 DEG C, the N of 100ml/min2Lower purging 2h, is down to room temperature；
In this process, first absorb, using 0.1M sodium hydrate aqueous solution, the titanium tetrachloride gases not participating in reaction, then
Continue to absorb titanium tetrachloride gases with activated carbon；
(3) under air atmosphere, 500 DEG C of roasting 5h are warming up to 10 DEG C/min, obtain silica gel load titanium catalyst.See figure
1.
The specific surface area of this silica gel load titanium catalyst is 181.4m2/ g, aperture isPore volume is 1.25cm3/ g, titanium
Load capacity be 1.68%.
Embodiment 5
The preparation method of silica gel load titanium catalyst, comprises the steps：
(1) method of embodiment 2 prepares unformed silica gel particle；
(2) unformed silica gel particle is placed in chemical vapor deposition unit, is warming up to 200 DEG C, in the N of 200ml/min2
Protection is lower to purge 1.5h, removes moisture；By liquid TiCl4It is heated to 30 DEG C, be passed through described after being sufficiently mixed with nitrogen after gasification
In chemical vapor deposition unit, TiCl4The flow of steam is 0.05ml/min, and nitrogen flow is 50ml/min, is warming up to 600
DEG C, react 3h；Chemical vapor deposition unit is cooled to 200 DEG C, the N of 50ml/min2Lower purging 2.5h, is down to room temperature；
In this process, first absorb, using 0.1M sodium hydrate aqueous solution, the titanium tetrachloride gases not participating in reaction, then
Continue to absorb titanium tetrachloride gases with activated carbon；
(3) under air atmosphere, 400 DEG C of roasting 6h are warming up to 15 DEG C/min, obtain silica gel load titanium catalyst.
The specific surface area of this silica gel load titanium catalyst is 153.6m2/ g, aperture isPore volume is 1.11cm3/ g, titanium
Load capacity be 1.30%.
Embodiment 6
The preparation method of silica gel load titanium catalyst, comprises the steps：
(1) method of embodiment 3 prepares unformed silica gel particle；
(2) unformed silica gel particle is placed in chemical vapor deposition unit, is warming up to 500 DEG C, in the N of 50ml/min2
Protection is lower to purge 1h, removes moisture；By liquid TiCl4It is heated to 100 DEG C, after being sufficiently mixed with nitrogen after gasification, be passed through describedization
Learn in vapor phase growing apparatus, TiCl4The flow of steam is 0.5ml/min, and nitrogen flow is 50ml/min, is warming up to 1000 DEG C,
Reaction 1h；Chemical vapor deposition unit is cooled to 500 DEG C, the N of 200ml/min2Lower purging 2h, is down to room temperature；
In this process, first absorb, using 0.1M sodium hydrate aqueous solution, the titanium tetrachloride gases not participating in reaction, then
Continue to absorb titanium tetrachloride gases with activated carbon；
(3) under air atmosphere, 600 DEG C of roasting 4h are warming up to 5 DEG C/min, obtain silica gel load titanium catalyst.
The specific surface area of this silica gel load titanium catalyst is 123.6m2/ g, aperture isPore volume is 0.81cm3/ g, titanium
Load capacity be 1.39%.
Embodiment 7
The silica gel load titanium catalyst of embodiment 4 aoxidizes, in catalysis Propylene Selectivity, the purposes that a step prepares expoxy propane,
Comprise the steps：
In fixed bed, in proportion, put into 0.5g silica gel load titanium catalyst, be former with propylene, cumyl hydroperoxide
Material, cumyl hydroperoxide is dissolved in isopropylbenzene, and at 80 DEG C, reaction pressure is 5MPa, and air speed controls in 10h-1, react 6h
Generate expoxy propane；The mol ratio of described cumyl hydroperoxide, propylene and isopropylbenzene is 1:5:30, described silica gel loading titanium is urged
Agent is 3 with the mass ratio of cumyl hydroperoxide:10.By-product 2- phenyl -2- propanol is through being dehydrated, being hydrogenated with, being oxidized to
Hydrogen oxide isopropylbenzene Posterior circle uses.Reaction result is shown in Table 1.
Table 1
Embodiment 8
The silica gel load titanium catalyst of embodiment 5 aoxidizes, in catalysis Propylene Selectivity, the purposes that a step prepares expoxy propane,
Comprise the steps：
In fixed bed, in proportion, put into 0.5g silica gel load titanium catalyst, be former with propylene, cumyl hydroperoxide
Material, cumyl hydroperoxide is dissolved in isopropylbenzene, and at 50 DEG C, reaction pressure is 0.1MPa, and air speed controls in 1h-1, reaction
12h generates expoxy propane；The mol ratio of described cumyl hydroperoxide, propylene and isopropylbenzene is 1:1:4, described silica gel loading titanium
Catalyst is 1 with the mass ratio of cumyl hydroperoxide:10.By-product 2- phenyl -2- propanol is through being dehydrated, being hydrogenated with, being oxidized to
Cumyl hydroperoxide Posterior circle uses.Reaction result is shown in Table 2.
Table 2
Embodiment 9
The silica gel load titanium catalyst of embodiment 6 aoxidizes, in catalysis Propylene Selectivity, the purposes that a step prepares expoxy propane,
Comprise the steps：
In fixed bed, in proportion, put into 0.5g silica gel load titanium catalyst, be former with propylene, cumyl hydroperoxide
Material, cumyl hydroperoxide is dissolved in isopropylbenzene, and at 110 DEG C, reaction pressure is 8MPa, and air speed controls in 5h-1, react 1h
Generate expoxy propane；The mol ratio of described cumyl hydroperoxide, propylene and isopropylbenzene is 1:10:50, described silica gel loading titanium
Catalyst is 5 with the mass ratio of cumyl hydroperoxide:10.By-product 2- phenyl -2- propanol is through being dehydrated, being hydrogenated with, being oxidized to
Cumyl hydroperoxide Posterior circle uses.Reaction result is shown in Table 3.
Table 3
Claims (5)
1. a kind of silica gel load titanium catalyst, is characterized in that the unformed silica gel particle of carrier is loaded with TiO2.
2. the preparation method of claim 1 silica gel load titanium catalyst, is characterized in that comprising the steps：
(1) unformed silica gel powder is shaped to unformed silica gel particle；
(2) unformed silica gel particle is placed in chemical vapor deposition unit, is warming up to 200-500 DEG C, in 50-200ml/min
N2Protection is lower to purge at least 1h, removes moisture；By liquid TiCl4It is heated to 30～100 DEG C, be sufficiently mixed with nitrogen after gasification
After be passed through in described chemical vapor deposition unit, TiCl4The flow of steam is (0.05-0.5) ml/min, and nitrogen flow is
50ml/min, is warming up to 600-1000 DEG C, reacts 1～3h；Chemical vapor deposition unit is cooled to 200-500 DEG C, 50-
The N of 200ml/min2Lower purging at least 2h, is down to room temperature；
(3) under air atmosphere, 400-600 DEG C of roasting 4-6h be warming up to 5-15 DEG C/min, obtain silica gel load titanium catalyst.
3. method according to claim 2, is characterized in that unformed silica gel powder is shaped to the step of unformed silica gel particle
Suddenly it is：
By unformed rubber powder end and boehmite 60-90 in mass ratio:The ratio of 10-40 mixes in kneader and must mix
Thing, adds the aqueous solution of nitric acid that mass concentration is 2%-10%, the ratio of described mixture and described aqueous solution of nitric acid is 10g:
5-10mL, stirring mixing, it is extruded into strip, 70-110 DEG C of drying 8-12h, under air conditionses, in 500-550 DEG C of roasting 3-5h, grind
Wear into granule, cross 30-40 mesh sieve, obtain unformed silica gel particle.
4. claim 1 silica gel load titanium catalyst aoxidizes, in catalysis Propylene Selectivity, the purposes that a step prepares expoxy propane.
5. purposes according to claim 4, is characterized in that comprising the steps：In fixed bed, in proportion, put into 0.5g
Silica gel load titanium catalyst, with propylene, cumyl hydroperoxide as raw material, cumyl hydroperoxide is dissolved in isopropylbenzene,
At 50-110 DEG C, reaction pressure is 0.1-8MPa, and air speed controls in 1-10h-1, reaction 1-12h generation expoxy propane；Described peroxide
The mol ratio changing hydrogen isopropylbenzene, propylene and isopropylbenzene is 1:1-10:4-50, described silica gel load titanium catalyst is different with hydrogen peroxide
The mass ratio of propyl benzene is 1-5:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735457.6A CN106378122A (en) | 2016-08-26 | 2016-08-26 | Silica gel loaded titanium catalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735457.6A CN106378122A (en) | 2016-08-26 | 2016-08-26 | Silica gel loaded titanium catalyst, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106378122A true CN106378122A (en) | 2017-02-08 |
Family
ID=57917186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610735457.6A Pending CN106378122A (en) | 2016-08-26 | 2016-08-26 | Silica gel loaded titanium catalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106378122A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107224993A (en) * | 2017-05-25 | 2017-10-03 | 万华化学集团股份有限公司 | A kind of preparation method of olefin epoxidation catalysts |
| CN107999139A (en) * | 2017-11-27 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity |
| CN107999140A (en) * | 2017-11-29 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for reducing vinyl chloride synthesis reaction temperature |
| CN109364980A (en) * | 2018-11-13 | 2019-02-22 | 湘潭大学 | A kind of preparation method and application preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium |
| WO2021103437A1 (en) * | 2019-11-26 | 2021-06-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene epoxide and a preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375358A (en) * | 2002-03-22 | 2002-10-23 | 深圳市尊业纳米材料有限公司 | Microporous nano composite material |
| CN1438919A (en) * | 2000-06-21 | 2003-08-27 | 国际壳牌研究有限公司 | Catalyst composition, process for its preparation and use thereof |
| CN1695800A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing load type photocatalyst of titania modified by Argentine |
-
2016
- 2016-08-26 CN CN201610735457.6A patent/CN106378122A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438919A (en) * | 2000-06-21 | 2003-08-27 | 国际壳牌研究有限公司 | Catalyst composition, process for its preparation and use thereof |
| CN1375358A (en) * | 2002-03-22 | 2002-10-23 | 深圳市尊业纳米材料有限公司 | Microporous nano composite material |
| CN1695800A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing load type photocatalyst of titania modified by Argentine |
Non-Patent Citations (2)
| Title |
|---|
| R. LEBODA ET AL，: "Structure of Chemical Vapor Deposition Titania/Silica Gel", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 赵红花等: "负载型TiO2光催化降解含酚废水的研究", 《兰州理工大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107224993A (en) * | 2017-05-25 | 2017-10-03 | 万华化学集团股份有限公司 | A kind of preparation method of olefin epoxidation catalysts |
| WO2018214931A1 (en) * | 2017-05-25 | 2018-11-29 | 万华化学集团股份有限公司 | Preparation method for olefin epoxidation catalyst and applications thereof |
| US11213811B2 (en) | 2017-05-25 | 2022-01-04 | Wanhua Chemical Group Co., Ltd. | Preparation method for olefin epoxidation catalyst and applications thereof |
| CN107999139A (en) * | 2017-11-27 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for improving vinyl chloride crude product purity |
| CN107999139B (en) * | 2017-11-27 | 2020-07-21 | 宁夏新龙蓝天科技股份有限公司 | Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product |
| CN107999140A (en) * | 2017-11-29 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for reducing vinyl chloride synthesis reaction temperature |
| CN109364980A (en) * | 2018-11-13 | 2019-02-22 | 湘潭大学 | A kind of preparation method and application preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium |
| WO2021103437A1 (en) * | 2019-11-26 | 2021-06-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene epoxide and a preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106378122A (en) | Silica gel loaded titanium catalyst, preparation method and application thereof | |
| Zhou et al. | Synthesis of stable heterogeneous catalysts by supporting carbon-stabilized palladium nanoparticles on MOFs | |
| CN105017529B (en) | A kind of preparation method of hierarchical porous structure covalent triazine class skeleton microporous polymer | |
| Dai et al. | Nanoporous N-doped Carbon/ZnO hybrid derived from zinc aspartate: An acid-base bifunctional catalyst for efficient fixation of carbon dioxide into cyclic carbonates | |
| Chen et al. | Salt-assisted synthesis of hollow Bi2WO6 microspheres with superior photocatalytic activity for NO removal | |
| CN108786779B (en) | Graphite alkyne/porous titanium dioxide photocatalyst and preparation method and application thereof | |
| CN108786874A (en) | Load the graphite phase carbon nitride nanometer sheet material and its preparation method and application of manganese dioxide | |
| CN108262034B (en) | Catalyst, preparation method thereof and application thereof in ammonia synthesis under normal pressure and low temperature | |
| CN106345469B (en) | A kind of dendroid Cu/C-CuSiO3 nanostructure hydrogenation catalyst preparation method | |
| CN113522317B (en) | Preparation method and application of cobalt-based bimetallic sulfur/carbon catalyst derived from MOFs (metal-organic frameworks) | |
| Alivand et al. | Defect engineering-induced porosity in graphene quantum dots embedded metal-organic frameworks for enhanced benzene and toluene adsorption | |
| Lin et al. | Salt-templated synthesis of Ce/Al catalysts supported on mesoporous silica for acetone oxidation | |
| KR20160010151A (en) | Catalyst for decomposition and regeneration of formic acid and method for preparing the same | |
| Zhu et al. | Efficient photocatalytic water splitting through titanium silicalite stabilized CoO nanodots | |
| Zhang et al. | Encapsulation of Au nanoparticles with well-crystallized anatase TiO 2 mesoporous hollow spheres for increased thermal stability | |
| CN109950563B (en) | Non-noble metal oxygen reduction reaction catalyst with high-dispersion metal active sites and preparation method thereof | |
| CN108191631A (en) | A kind of method based on CdS photocatalytic reduction of carbon oxide | |
| CN103395822B (en) | A kind of Red copper oxide micrometre hollow sphere and synthetic method, application method | |
| KR20160142135A (en) | Catalysts for ammonia dehydrogenation, methods of producing the same, and methods of producing hydrogen gas from ammonia using the same | |
| CN107308967B (en) | Catalyst promoter for photocatalytic decomposition of formic acid to produce hydrogen, photocatalytic system and method for decomposing formic acid to produce hydrogen | |
| Li et al. | Recent advance of atomically dispersed dual‐metal sites carbocatalysts: Properties, synthetic materials, catalytic mechanisms, and applications in persulfate‐based advanced oxidation process | |
| Park et al. | Ti-Based porous materials for reactive oxygen species-mediated photocatalytic reactions | |
| Zhuang et al. | Mesoporous carbon-supported cobalt catalyst for selective oxidation of toluene and degradation of water contaminants | |
| CN1234928C (en) | Preparing method for titanium dioxide fibre | |
| Cui et al. | Synthesis and characterization of mesoporous sodalite and investigation of the effects of inorganic salts on its structure and properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170208 |
|
| WD01 | Invention patent application deemed withdrawn after publication |