CN106378182A - An efficient titanium silicalite molecular sieve catalyst - Google Patents
An efficient titanium silicalite molecular sieve catalyst Download PDFInfo
- Publication number
- CN106378182A CN106378182A CN201610689312.7A CN201610689312A CN106378182A CN 106378182 A CN106378182 A CN 106378182A CN 201610689312 A CN201610689312 A CN 201610689312A CN 106378182 A CN106378182 A CN 106378182A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium
- catalyst
- sieve catalyst
- efficient
- 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
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an efficient titanium silicalite molecular sieve catalyst. The catalyst comprises a silicon source, a titanium source, a template, a mineralizer and a solvent, wherein the silicon source is Si(OR1)4, (R2O)<3>Si-(CH2)<n1>-Si(OR3)<3> and (R4)<n2>Si(OR5)<4-n2>, the titanium source is Ti(OR6)4, the template is [(CH3)<3>CH<3>(CH2)<n3>N<+>]X<->, the mineralizer is [(CH3C<n4>H<2n4>)<4>NH<4>]<+>OH<->, and the solvent is a mixture of water and ethanol. The molecular sieve structure comprises hydrophobic and carbon-deposition-preventing organic functional groups and composite pores, and therefore the catalyst has excellent hydrophobicity and mass transfer performance, high activity, high selectivity and high stability, and the catalyst can be used for alkene epoxidation processes adopting H2O2, 1-hydroperoxyethylbenzene, cumene hydroperoxide, tert-butyl hydroperoxide, and the like as oxidants to produce corresponding epoxides.
Description
Technical field
The invention belongs to chemical technology field, it is related to a kind of efficient titanium-silicon molecular sieve catalyst, specifically, particularly to passing through
Hydrothermal crystallizing method is by four-coordination active titanium species and the Si- (CH containing organo-functional group2)n1-Si、Si-O-Si(R4)n2With
Ti-O-Si(R4)n2Assemble in situ is in the efficient titanium-silicon molecular sieve catalyst with composite pore structural.
Background technology
Titanium porous molecular sieve materials are respectively provided with to hydroxylating of selective oxidation, the ammoxidation of ketone/aldehyde and aromatic hydrocarbons of hydro carbons etc.
Good catalysis activity, can be as the catalyst of alkene epoxidation and other multiple reaction, before having wide commercial Application
Scape.
Through retrieval, patent US4410501 makes public for the first time the synthetic method of TS-1 molecular sieve.The method is with tetrapropyl hydrogen-oxygen
Aqueous solution, organic titanate and the organosilicon acid esters of changing ammonium prepare titanium silicon mixed colloidal solution for raw material, then brilliant by hydro-thermal
It is combined to HTS.Because TS-1 molecular sieve is incorporated into molecule sieve skeleton the transition metal titanium atom with feature of appraising at the current rate
Frame, defines the oxidation reduction catalyst with selectional feature, has good catalytic oxidation performance.This molecular sieve is from 1983
Since year synthesizes first, with H2O2Ammoxidation for the ketone of oxidant（EP 0267362）, alkene epoxidation（EP
1100119）, the hydroxylating of aromatic hydrocarbons（US 4396783）Show good commercial application potentiality in field.
For the epoxidation reaction of olefin and its derivatives, because TS-1 is the micro-pore zeolite with MFI structure, aperture
It is about 0.55nm, be limited to the use of with H2O2Prepare in the technique of expoxy propane for oxidizer catalytic epoxidation propylene.When with larger chi
Very little organic peroxide, such as hydrogen peroxide ethylbenzene and cumyl hydroperoxide are oxidizing propylene and bigger alkene
When, TS-1 does not almost have catalysis activity.And with H2O2For oxidant, TS-1 molecular sieve is the Selective Oxidation of catalyst
In it is desirable to catalyst has certain hydrophobicity, the organic reactant being easy to make to have hydrophobic property adsorbs in catalyst surface
On reacted, and the heavier component generating is difficult the activity and the stability that adhere to and affect catalyst on a catalyst.Logical
In the case of often, prepared HTS has certain hydrophobicity, but this hydrophobicity is relatively weak, does not have to generation
Heavier component molten carbon ability, catalyst easily inactivates, and stability is poor.
When patent US 4367342 and US3923843 disclose with the amorphous silica of titaniferous for catalyst, peroxide
Changing hydrogen ethylbenzene can be expoxy propane by epoxidation of propylene.But the amorphous silica carrier specific surface area by being adopted is little,
Ti content is low, and catalyst surface hydrophobicity is poor, and product expoxy propane is easily gather in its surface ring opening hydrolysis and further
Symphysis becomes the polymer of larger molecular weight to be attached to catalyst surface, affects the selectivity to expoxy propane for the catalyst, goes forward side by side
One step causes catalyst to inactivate.Therefore, such catalyst cannot be competent at macrocyclic efficient propylene catalytic epoxidation system.
Patent CN1500004A and CN 1248579A disclose with cumyl hydroperoxide or hydrogen peroxide ethylbenzene for oxidation
Agent, Selective Oxidation of Propylene can be become expoxy propane by Ti-MCM41 mesoporous molecular sieve catalyst.But for improving Ti-MCM41 catalysis
The hydrophobicity of agent, after molecular sieve catalyst end of synthesis, needs using sillylation reagent, catalyst to be carried out additionally
Silylanizing process so that the production process of catalyst is loaded down with trivial details, inefficiency, manufacturing cost is high.
Through retrieval it was found that Nature magazine（1994, 368, 321）Describe another and there is meso-hole structure spy
The titanium-containing molecular sieve catalyst levied（Ti-HMS）.Compared with Ti-MCM41, Ti-HMS has superior technique economy.But Ti-
, due to catalyst active center's skewness, surface hydrophobic is poor, with organic peroxide as oxidant for HMS catalysis material
When carrying out alkene epoxidation, product yield is low, poor catalyst stability, and deactivation rate is fast.
Therefore, for efficient titanium-silicon molecular sieve catalyst, in particular for the efficient titanium silicon of epoxidation reaction of olefines
Molecular sieve catalyst, in addition to the existence form of titanium species, its pore passage structure and surface hydrophobic are also to affect its catalytic performance
Key factor.Pore passage structure determines applicable raw material and product molecule size, and surface hydrophobic determines the choosing of product
Selecting property.Therefore, fabricated in situ has composite pore structural and the good new and effective titanium-silicon molecular sieve catalyst of surface hydrophobic is
The developing direction of olefin epoxidation catalysts.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of aperture big, and has the height of excellent selectivity and stability
Effect titanium-silicon molecular sieve catalyst.
For solving above-mentioned technical problem, the technical scheme is that：It is by silicon source, titanium source, template, mineralizer and
Solvent forms；Described silicon source is Si (OR1)4、(R2O)3Si-(CH2)n1-Si(OR3)3(R4)n2Si(OR5)4-n2, titanium source is Ti
(OR6)4, template is [(CH3)3CH3(CH2)n3N+]X-, mineralizer is [(CH3Cn4H2n4)4NH4]+OH-, solvent be water and
Ethanol is according to 1:The mixture of 1 volume ratio composition；And above-mentioned each material has following molar relationship：[(CH3)3CH3
(CH2)n3N+]X-: [(CH3Cn4H2n4)4NH4]+OH-:Si(OR1)4:(R2O)3Si-(CH2)n1-Si(OR3)3: (R4)n2Si
(OR5)4-n2:Ti(OR6)4:H2O=0.1～1:0.1～2:1:0.01～2:0.01～1.0:0.01～0.1:2～20；Its
In, R1～R6For positive alkylene；n1For 1 and 2；n2Integer for 1～3；n3Integer for 12～18；n4Integer for 1～3；X is
I.
Further, the ultraviolet-visible spectrum spectrogram of described efficient titanium-silicon molecular sieve catalyst is between 200～240nm
Comprise an absworption peak being attributed to four-coordination titanium species, do not have absworption peak to occur in other positions；Its infrared spectrum spectrogram exists
940～970cm-1Between comprise one and be attributed to the absworption peak relevant with four-coordination titanium.
It is an advantage of the current invention that：
（1）The efficient titanium-silicon molecular sieve catalyst of the present invention, the quaternary ammonium salt using bigger molecule size is template so as to have
Under the mineralization of machine ammonium hydroxide, fabricated in situ contains the composite holes catalysis material of mesopore-macropore structure, makes it possible to be suitable for
In olefin hydrocarbon molecules and the corresponding epoxidation product of different molecular size, and solve mass transfer problem；Secondly, with containing organic functional
The silicon source part of group substitutes esters of silicon acis, makes the HTS of synthesis not only have Si-O-Si key, Si-O-Ti key, but also has
There is hydrophobic and molten carbon functional Si- (CH2)n1-Si、Si-O-Si(R4)n2With Ti-O-Si (R4)n2Functional group, so that catalyst
There is excellent selectivity and stability；
（2）The synthetic method of the efficient titanium-silicon molecular sieve catalyst of the present invention, is loaded into active titanium species and organic official using original position
The one-step method for synthesizing that can roll into a ball, significantly reduces production cost and the production cycle of molecular sieve catalyst, makes industrialized production more
Feasible and economy.
Specific embodiment
The following examples can make professional and technical personnel that the present invention is more fully understood, but not therefore by this
Bright it is limited among described scope of embodiments.
Embodiment 1
Under the gentle agitation of room, by account for intend totalling amount 70% silicon source tetraethyl orthosilicate, two（Triethoxysilyl）Methane
It is added to template cetyl trimethylammonium bromide, mineralizer tetraethyl hydroxide with the mixed solution of trimethyoxysilane
It is hydrolyzed in the mixed solution of ammonium and water, form colourless transparent solution I；By remaining 30% silicon source tetraethyl orthosilicate, two
（Triethoxysilyl）Shape is fully mixed with titanium source butyl titanate again after methane and trimethyoxysilane mixing
Become mixed solution II；Under -5 DEG C and quick stirring, solution II is slowly added in solution I, forms light yellow transparent solution,
And continue to stir 1 hour, it is designated as solution III；Solution III is transferred to and in stainless steel autoclave, carries out Crystallizing treatment, crystallization temperature
140 DEG C, crystallization time 72 hours.It is 7～8, Ran Hou that molecular sieve after crystallization is carried out filtering, washing to the pH value of filtrate
Dry 12 hours for 110 DEG C, 550 DEG C of roastings 5 hours, obtain final product the efficient titanium-silicon molecular sieve catalyst of composite holes of very hydrophobic.
During above-mentioned system with molecular sieve for preparing is standby, the component relationship of the amount of each material is [(CH3)3CH3(CH2)15N+]Br-:
[(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2-Si(OC2H5)3: CH3Si(OCH3)3:Ti(OC4H9)4:H2O
=0.3:0.4:1:0.3: 0.1:0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrum spectrogram in 215 nm about have stronger
Absworption peak, does not have absworption peak to exist at other wavelength.It is infrared（FT-IR）Spectrum spectrogram is in 960cm-1Place has one significantly to inhale
Receive peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 2
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, reduce the addition of butyl titanate.The amount of each material
Component relationship is [(CH3)3CH3(CH2)15N+]Br-: [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2-Si
(OC2H5)3: CH3Si(OCH3)3:Ti(OC4H9)4:H2O =0.3:0.4:1:0.3: 0.1:0.03:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrum spectrogram in 215 nm about have stronger
Absworption peak, does not have absworption peak to exist at other wavelength.It is infrared（FT-IR）Spectrum spectrogram is in 960cm-1Place has one significantly to inhale
Receive peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 3
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, reduce (C2H5O)3Si-CH2-Si(OC2H5)3Addition.
The component relationship of the amount of each material is [(CH3)3CH3(CH2)15N+]Br-: [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:
(C2H5O)3Si-CH2-Si(OC2H5)3: CH3Si(OCH3)3:Ti(OC4H9)4:H2O =0.3:0.4:1:0.2: 0.1:0.04:
10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrogram in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared spectrum spectrogram（FT-IR）In 960cm-1Place has one significantly to absorb
Peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 4
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, the addition of adjustment template and mineralizer.Each material
The component relationship of amount is [(CH3)3CH3(CH2)15N+]Br-: [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-
CH2-Si(OC2H5)3: CH3Si(OCH3)3:Ti(OC4H9)4:H2O =0.4:0.3:1:0.3: 0.1:0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrogram in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared spectrum spectrogram（FT-IR）In 960cm-1Place has one significantly to absorb
Peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 5
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, by (C2H5O)3Si-CH2-Si(OC2H5)3Replace with
(C2H5O)3Si-CH2CH2-Si(OC2H5)3, the component relationship of the amount of each material is：[(CH3)3CH3(CH2)15N+]Br-:
[(CH3CH2)4NH4]+OH-:Si(OC2H5)4:(C2H5O)3Si-CH2CH2-Si(OC2H5)3: CH3Si(OCH3)3:Ti(OC4H9)4:
H2O =0.3:0.4:1:0.3: 0.1:0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrogram in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared spectrum spectrogram（FT-IR）In 960cm-1Place has one significantly to absorb
Peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 6
Compared with embodiment 1, simply during system with molecular sieve for preparing is standby, by CH3Si(OCH3)3Replace with (CH3)2Si(OCH3)2, respectively
The component relationship of the amount of material is：[(CH3)3CH3(CH2)15N+]Br-: [(CH3CH2)4NH4]+OH-:Si(OC2H5)4:
(C2H5O)3Si-CH2-Si(OC2H5)3: (CH3)2Si(OCH3)2:Ti(OC4H9)4:H2O =0.3:0.4:1:0.3: 0.1:
0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrum spectrogram in 215 nm about have stronger
Absworption peak, does not have absworption peak to exist at other wavelength.It is infrared（FT-IR）Spectrum spectrogram is in 960cm-1Place has one significantly to inhale
Receive peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 7～9
Performance evaluation is carried out to the efficient titanium-silicon molecular sieve catalyst prepared by embodiment 1～3：In a band mechanical agitation with outward
Carry out in the 1L stainless steel autoclave of chuck heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.
The ethylbenzene solution of the hydrogen peroxide ethylbenzene (EBHP) being 30% with weight concentration as oxidant, the addition of 30wt%EBHP oxidation solution
For 400g, the addition of propylene is 185g, and the addition of efficient titanium-silicon molecular sieve catalyst is 8 g, 95 DEG C of reaction temperature, reaction
Pressure 3.6MPa, response time 3h.Efficiently the catalytic performance test of titanium-silicon molecular sieve catalyst the results are shown in Table 1.
In table 1, the result of embodiment 7～9 corresponds respectively to the efficient titanium molecular sieve catalysis as prepared by embodiment 1～3
Agent.
Embodiment 10～12
Performance evaluation is carried out to the efficient titanium-silicon molecular sieve catalyst prepared by embodiment 4～6：In a band mechanical agitation with outward
Carry out in the 1L stainless steel autoclave of chuck heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.
The cumene solution of the cumyl hydroperoxide (CHP) being 40% with weight concentration as oxidant, the addition of 40wt%CHP oxidation solution
Measure as 350g, the addition of propylene is 195g, the addition of efficient titanium-silicon molecular sieve catalyst is 10 g, and reaction temperature is 90
DEG C, reaction pressure 3.5MPa, the response time is 3h.Efficiently the catalytic performance test of titanium-silicon molecular sieve catalyst the results are shown in Table 2.
The efficient HTS that in table 2, the result of embodiment 10～12 corresponds respectively to as prepared by embodiment 4～6 is urged
Agent.
Embodiment 13～15
Performance evaluation is carried out to the efficient titanium-silicon molecular sieve catalyst prepared by embodiment 1～3：In a band mechanical agitation with outward
Carry out in the 1L stainless steel autoclave of chuck heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.
The ethylbenzene solution of the hydrogen peroxide ethylbenzene (EBHP) being 30% with weight concentration as oxidant, the addition of 30wt%EBHP oxidation solution
For 350g, the addition of 1-butylene is 215g, and the addition of efficient titanium-silicon molecular sieve catalyst is 7.5 g, 90 DEG C of reaction temperature,
Reaction pressure 2.5MPa, response time 3h.Efficiently the catalytic performance test of titanium-silicon molecular sieve catalyst the results are shown in Table 3.
The efficient HTS that in table 3, the result of embodiment 13～15 corresponds respectively to as prepared by embodiment 1～3 is urged
Agent.
Comparative example 1
Under the gentle agitation of room, it is added to template cetyl front three by accounting for the silicon source tetraethyl orthosilicate intending totalling amount 70%
It is hydrolyzed in the mixed solution of base ammonium bromide, mineralizer tetraethyl ammonium hydroxide and water, form colourless transparent solution I；To remain
Remaining 30% silicon source tetraethyl orthosilicate and titanium source butyl titanate carries out being mixed thoroughly to form mixed solution II；At -5 DEG C with soon
Under speed stirring, solution II is slowly added in solution I, forms light yellow transparent solution, and continue to stir 1 hour, be designated as molten
Liquid III；Solution III is transferred to and in stainless steel autoclave, carries out Crystallizing treatment, 140 DEG C of crystallization temperature, crystallization time 72 hours；Will
It is 7～8 that molecular sieve after crystallization carries out filtering, washing to the pH value of filtrate, then dries 12 hours at 110 DEG C, 550 DEG C of roastings
5 hours, that is, it is obtained and contrasts efficient titanium-silicon molecular sieve catalyst.
During above-mentioned system with molecular sieve for preparing is standby, the component relationship of the amount of each material is [(CH3)3CH3(CH2)15N+]Br-:
[(CH3CH2)4NH4]+OH-:Si(OC2H5)4: Ti(OC4H9)4:H2O =0.3:0.4:1:0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrum spectrogram in 220 nm about have stronger
Absworption peak, also with the presence of a weaker absworption peak at 260nm.It is infrared（FT-IR）Spectrum spectrogram is in 960cm-1Place has one bright
Aobvious absworption peak.The aperture size in more than 85% hole is more than 2nm.
Comparative example 2
Compared with comparative example 1, simply template cetyl trimethylammonium bromide is replaced with Tetradecyl Trimethyl Ammonium Bromide,
Mineralizer tetraethyl ammonium hydroxide replaces with Tetramethylammonium hydroxide, other constant.
The component relationship of the amount of each material is [(CH3)3CH3(CH2)13N+]Br-: [(CH3)4NH4]+OH-:Si
(OC2H5)4: Ti(OC4H9)4:H2O =0.3:0.4:1:0.04:10（Mol ratio）.
The ultraviolet-visible of this efficient titanium-silicon molecular sieve catalyst（UV-Vis）Spectrogram in 220 nm about have stronger absorption
Peak, also with the presence of a weaker absworption peak at 260nm.Its infrared spectrum spectrogram（FT-IR）In 960cm-1Place has one obvious
Absworption peak.The aperture size in more than 80% hole is more than 2nm.
Comparative example 3,4
Efficient titanium-silicon molecular sieve catalyst as prepared by comparative example 1,2 is carried out catalytic by the evaluation methodology of embodiment 7～9
Can evaluate, evaluation result is shown in Table 1.In table 1, the result of comparative example 3,4 corresponds respectively to the efficient titanium as prepared by comparative example 1,2
Silicalite molecular sieve catalyst.
Comparative example 5,6
Efficient titanium-silicon molecular sieve catalyst as prepared by comparative example 1,2 is catalyzed by the evaluation methodology of embodiment 10～12
Performance evaluation, evaluation result is shown in Table 2.In table 2 result of comparative example 5,6 correspond respectively to efficient as prepared by comparative example 1,2
Titanium-silicon molecular sieve catalyst.
Table 1
As can be seen from the above table, the efficient titanium silicon molecule of the efficient titanium-silicon molecular sieve catalyst of embodiment 1～3 and comparative example 1 and 2
Sieve catalyst is compared, and its catalyst performance is better than comparative example, and EBHP conversion ratio and expoxy propane select equal ＞ 99%.
Table 2
As can be seen from the above table, the efficient titanium silicon molecule of the efficient titanium-silicon molecular sieve catalyst of embodiment 4～6 and comparative example 1 and 2
Sieve catalyst is compared, and its catalyst performance is better than comparative example, and EBHP conversion ratio and expoxy propane select equal ＞ 99%.
Table 3
As can be seen from the above table, the catalyst performance of the efficient titanium-silicon molecular sieve catalyst of embodiment 1～3 is more excellent, and its EBHP turns
Rate and epoxy butane select equal ＞ 99%.
Ultimate principle and principal character and the advantages of the present invention of the present invention have been shown and described above.The skill of the industry
The simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description for the art personnel
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.Claimed scope by appending claims and
Its equivalent thereof.
Claims (2)
1. a kind of efficient titanium-silicon molecular sieve catalyst, it is made up of silicon source, titanium source, template, mineralizer and solvent；It is special
Levy and be：Described silicon source is Si (OR1)4、(R2O)3Si-(CH2)n1-Si(OR3)3(R4)n2Si(OR5)4-n2, titanium source is Ti
(OR6)4, template is [(CH3)3CH3(CH2)n3N+]X-, mineralizer is [(CH3Cn4H2n4)4NH4]+OH-, solvent be water and
Ethanol is according to 1:The mixture of 1 volume ratio composition；And above-mentioned each material has following molar relationship：[(CH3)3CH3
(CH2)n3N+]X-: [(CH3Cn4H2n4)4NH4]+OH-:Si(OR1)4:(R2O)3Si-(CH2)n1-Si(OR3)3: (R4)n2Si
(OR5)4-n2:Ti(OR6)4:H2O=0.1～1:0.1～2:1:0.01～2:0.01～1.0:0.01～0.1:2～20；Its
In, R1～R6For positive alkylene；n1For 1 and 2；n2Integer for 1～3；n3Integer for 12～18；n4Integer for 1～3；X is
I.
2. efficient titanium-silicon molecular sieve catalyst according to claim 1 it is characterised in that：Described efficient HTS
The ultraviolet-visible spectrum spectrogram of catalyst comprises an absworption peak being attributed to four-coordination titanium species between 200～240nm,
Absworption peak is not had to occur in other positions；Its infrared spectrum spectrogram is in 940～970cm-1Between comprise one and be attributed to join with four
The relevant absworption peak of position titanium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610689312.7A CN106378182A (en) | 2016-08-19 | 2016-08-19 | An efficient titanium silicalite molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610689312.7A CN106378182A (en) | 2016-08-19 | 2016-08-19 | An efficient titanium silicalite molecular sieve catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106378182A true CN106378182A (en) | 2017-02-08 |
Family
ID=57916809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610689312.7A Pending CN106378182A (en) | 2016-08-19 | 2016-08-19 | An efficient titanium silicalite molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106378182A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019615A (en) * | 2018-08-29 | 2018-12-18 | 华东师范大学 | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle |
-
2016
- 2016-08-19 CN CN201610689312.7A patent/CN106378182A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019615A (en) * | 2018-08-29 | 2018-12-18 | 华东师范大学 | A kind of adjustable mesoporous SiO containing Ti of hydrophilic and hydrophobic2The preparation method of nano particle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101767036B (en) | Titanium silicalite TS-1 catalyst preparation method | |
| AU2010324184B2 (en) | Process for the manufacture of propylene oxide | |
| CN103030612B (en) | Method for producing epoxypropane through reaction between cumyl hydroperoxide and propylene | |
| CN101757945A (en) | Titanium-silicon molecular sieve TS-1 catalyst for catalyzing ketone oximation reaction | |
| CN101786638A (en) | Titanium silicate molecular sieve modification method | |
| CN105367520B (en) | The method for preparing expoxy propane | |
| CN106145151A (en) | A kind of multi-stage porous HTS and synthetic method thereof | |
| Yao et al. | Enhancing the accessible TiO6 concentration and the hydrophobicity of hierarchical TS-1 zeolites for alkene epoxidation and oxidative desulfurization | |
| Huali et al. | A review on heterogeneous solid catalysts and related catalytic mechanisms for epoxidation of olefins with H2O2 | |
| CN106378182A (en) | An efficient titanium silicalite molecular sieve catalyst | |
| CN104437636B (en) | Titaniferous porous silica Si catalyst, preparation method and its usage | |
| CN106111185A (en) | A kind of titanium-silicon molecular sieve catalyst and its preparation method and application | |
| CN106315607A (en) | Titanium silicate molecular sieve catalyst comprising organic functional group | |
| Farzaneh et al. | V-MCM-41 as selective catalyst for epoxidation of olefins and trans-2-hexene-1-ol | |
| CN106315608A (en) | Method for preparing efficient titanium silicalite molecular sieve catalyst | |
| CN106348311A (en) | Preparation method of titanium-silicalite-molecular-sieve catalyst | |
| CN106378183A (en) | A titanium silicalite molecular sieve catalyst | |
| CN106378181A (en) | A molecular sieve catalyst | |
| CN106378184A (en) | Application of molecular sieve catalyst | |
| CN106268941A (en) | A kind of preparation method of the titanium-silicon molecular sieve catalyst containing organo-functional group | |
| CN105085462B (en) | A kind of method of oxidizing cyclohexanone | |
| CN102807537B (en) | Method for preparing propylene oxide | |
| CN106316991A (en) | Application of titanium silicalite molecular sieve catalyst | |
| CN102807538B (en) | Method for preparing propylene oxide | |
| CN102875496B (en) | Method for producing cyclohexene oxide by reacting cumyl hydroperoxide with cyclohexene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170208 |
|
| WD01 | Invention patent application deemed withdrawn after publication |