CN106348311A - Preparation method of titanium-silicalite-molecular-sieve catalyst - Google Patents
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Abstract
The invention relates to a preparation method a titanium-silicalite-molecular-sieve catalyst. The preparation method includes: mixing and hydrolyzing a silicon source, a template agent, a mineralizing agent and water under normal temperature; slowly adding the mixture of a titanium source and the rest of silicone source into the silicon hydroxide solution after the hydrolyzing while fast stirring to perform gelatinization; transferring gel into a crystalizing kettle for crystallization; washing the crystalized molecular sieve, filtering, and calcining for 4-6 hours to remove the template agent so as to obtain the composite-pore titanium-silicalite-molecular-sieve catalyst, wherein calcining temperature is 500-600 DEG C. The preparation method has the advantages that the method is simple in process and high in preparation efficiency; due to the fact that the structure of the molecular sieve comprises hydrophobic and carbon-deposition-resistant organic functional groups and composite pores, the catalyst is excellent in hydrophobicity and mass transfer performance, high in activity and selectivity, good in stability and applicable to the olefin epoxidation production using H2O2, ethylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like to produce corresponding oxides.
Description
Technical field
The invention belongs to chemical technology field, it is related to a kind of preparation method of titanium-silicon molecular sieve catalyst, specifically, especially relates to
And by hydrothermal crystallizing method 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 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 (ep 0267362) for the ketone of oxidant, alkene epoxidation (ep
1100119), the field such as hydroxylating (us 4396783) of aromatic hydrocarbons has shown good commercial application potentiality.
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) describes another has meso-hole structure spy
The titanium-containing molecular sieve catalyst (ti-hms) levied.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 titanium-silicon molecular sieve catalyst, the HTS in particular for epoxidation reaction of olefines is urged
Agent, in addition to the existence form of titanium species, its pore passage structure and surface hydrophobic are also the key factor affecting its catalytic performance.
Pore passage structure determines applicable raw material and product molecule size, and surface hydrophobic determines the selectivity of product.Therefore,
Fabricated in situ has composite pore structural and the good novel titanosilicate catalyst of surface hydrophobic is alkene epoxidation catalysis
The developing direction of agent.
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 titanium of excellent selectivity and stability
The preparation method of silicalite molecular sieve catalyst.
For solving above-mentioned technical problem, the technical scheme is that described synthetic method comprises the steps: that (1) will
Silicon source si (or1)4、(r2o)3si-(ch2)n1-si(or3)3(r4)n2si(or5)4-n2The 1/4～4/5 of total amount and whole template
Agent [(ch3)3ch3(ch2)n3n+]x-, mineralizer [(ch3cn4h2n4)4nh4]+oh-And water carries out mixed hydrolysis at normal temperatures；(2)
After hydrolysis terminates, by titanium source ti (or6)4It is slowly added into the hydrogen-oxygen after hydrolysis with the mixture of remaining silicon source under fast stirring
In SiClx solution, carry out plastic, -5～60 DEG C of gelling temperature；(3) colloid is transferred to and in crystallizing kettle, carry out crystallization, crystallization temperature
100～160 DEG C, crystallization time 1～72 hour；(4) molecular sieve after crystallization is carried out washing, filters and roasting is to remove template
Agent, 500～600 DEG C of sintering temperature, roasting 4～6 hours, obtain final product composite holes titanium-silicon molecular sieve catalyst.
Further, the silicon source adding in described step (1) accounts for the 1/3～3/4 of silicon source total amount；In described step (2)
Gelling temperature is 10～30 DEG C；Crystallization temperature in described step (3) is 120 DEG C, and crystallization time is 12～40 hours；Described step
Suddenly the sintering temperature in (4) is 550 DEG C.
It is an advantage of the current invention that:
(1) titanium-silicon molecular sieve catalyst of the present invention, the quaternary ammonium salt using bigger molecule size is template so as in organic hydrogen
Under the mineralization of amine-oxides, fabricated in situ contains the composite holes catalysis material of mesopore-macropore structure, makes it possible to be applied to not
With olefin hydrocarbon molecules and the corresponding epoxidation product of molecular dimension, and solve mass transfer problem；Secondly, with containing organo-functional group
Silicon source part substitutes esters of silicon acis, makes the HTS of synthesis not only have si-o-si key, si-o-ti key, but also has thin
Water and molten carbon functional si- (ch2)n1-si、si-o-si(r4)n2With ti-o-si (r4)n2Functional group, so that catalyst has
Excellent selectivity and stability；
(2) synthetic method of the titanium-silicon molecular sieve catalyst of the present invention, is loaded into active titanium species and organo-functional group using original position
One-step method for synthesizing, significantly reduce production cost and the production cycle of molecular sieve catalyst, so that industrialized production more may be used
Row 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, the silicon source tetraethyl orthosilicate intending totalling amount 70%, two (triethoxysilyl) methane will be accounted for
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；By remaining 30% silicon source tetraethyl orthosilicate, two
Shape is fully mixed with titanium source butyl titanate again after (triethoxysilyl) methane and trimethyoxysilane mixing
Become mixed solution；Under -5 DEG C and quick stirring, solution is slowly added in solution, forms light yellow transparent solution,
And continue to stir 1 hour, it is designated as solution；Transfer the solution into and in stainless steel autoclave, carry 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 composite holes titanium-silicon molecular sieve catalyst 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).
Ultraviolet-visible (uv-vis) spectrum spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared (ft-ir) spectrum spectrogram is in 960cm-1Place has one significantly to absorb
Peak.95% 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).
Ultraviolet-visible (uv-vis) spectrum spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared (ft-ir) spectrum spectrogram is in 960cm-1Place has one significantly to absorb
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).
Ultraviolet-visible (uv-vis) spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absworption peak,
Absworption peak is not had to exist at other wavelength.Its infrared spectrum spectrogram (ft-ir) is in 960cm-1There is an obvious absworption peak at place.
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).
Ultraviolet-visible (uv-vis) spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absworption peak,
Absworption peak is not had to exist at other wavelength.Its infrared spectrum spectrogram (ft-ir) is in 960cm-1There is an obvious absworption peak at place.
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).
Ultraviolet-visible (uv-vis) spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absworption peak,
Absworption peak is not had to exist at other wavelength.Its infrared spectrum spectrogram (ft-ir) is in 960cm-1There is an obvious absworption peak at place.
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).
Ultraviolet-visible (uv-vis) spectrum spectrogram of this titanium-silicon molecular sieve catalyst in 215 nm about have stronger absorption
Peak, does not have absworption peak to exist at other wavelength.Its infrared (ft-ir) spectrum spectrogram is in 960cm-1Place has one significantly to absorb
Peak.The aperture size in more than 95% hole is more than 2nm.
Embodiment 7～9
Titanium-silicon molecular sieve catalyst prepared by embodiment 1～3 is carried out with performance evaluation: in a band mechanical agitation and external jacket
Carry out in the 1l stainless steel autoclave of heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.With weight
Amount concentration is the ethylbenzene solution of 30% hydrogen peroxide ethylbenzene (ebhp) is oxidant, and the addition of 30wt%ebhp oxidation solution is
400g, the addition of propylene is 185g, and the addition of titanium-silicon molecular sieve catalyst is 8 g, 95 DEG C of reaction temperature, reaction pressure
3.6mpa, response time 3h.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 titanium-silicon molecular sieve catalyst as prepared by embodiment 1～3.
Embodiment 10～12
Titanium-silicon molecular sieve catalyst prepared by embodiment 4～6 is carried out with performance evaluation: in a band mechanical agitation and external jacket
Carry out in the 1l stainless steel autoclave of heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.With weight
Amount concentration is the cumene solution of 40% cumyl hydroperoxide (chp) is oxidant, and the addition of 40wt%chp oxidation solution is
350g, the addition of propylene is 195g, and the addition of titanium-silicon molecular sieve catalyst is 10 g, and reaction temperature is 90 DEG C, reaction pressure
Power 3.5mpa, the response time is 3h.The catalytic performance test of titanium-silicon molecular sieve catalyst the results are shown in Table 2.
In table 2, the result of embodiment 10～12 corresponds respectively to the titanium molecular sieve catalysis as prepared by embodiment 4～6
Agent.
Embodiment 13～15
Titanium-silicon molecular sieve catalyst prepared by embodiment 1～3 is carried out with performance evaluation: in a band mechanical agitation and external jacket
Carry out in the 1l stainless steel autoclave of heating by electric cooker, reaction temperature is outer plus set electric furnace automatic temp controller is adjusted.With weight
Amount concentration is the ethylbenzene solution of 30% hydrogen peroxide ethylbenzene (ebhp) is oxidant, and the addition of 30wt%ebhp oxidation solution is
350g, the addition of 1-butylene is 215g, and the addition of titanium-silicon molecular sieve catalyst is 7.5 g, 90 DEG C of reaction temperature, reaction pressure
Power 2.5mpa, response time 3h.The catalytic performance test of titanium-silicon molecular sieve catalyst the results are shown in Table 3.
In table 3, the result of embodiment 13～15 corresponds respectively to the titanium molecular sieve catalysis as prepared by embodiment 1～3
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；To remain
Remaining 30% silicon source tetraethyl orthosilicate and titanium source butyl titanate carries out being mixed thoroughly to form mixed solution；At -5 DEG C with soon
Under speed stirring, solution is slowly added in solution, forms light yellow transparent solution, and continue to stir 1 hour, be designated as molten
Liquid；Transfer the solution into and in stainless steel autoclave, carry 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, contrast titanium-silicon molecular sieve catalyst is obtained.
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).
Ultraviolet-visible (uv-vis) spectrum spectrogram of this titanium-silicon molecular sieve catalyst in 220 nm about have stronger absorption
Peak, also with the presence of a weaker absworption peak at 260nm.Its infrared (ft-ir) spectrum spectrogram is in 960cm-1Place has one obvious
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).
Ultraviolet-visible (uv-vis) spectrogram of this titanium-silicon molecular sieve catalyst in 220 nm about have stronger absworption peak,
Also with the presence of a weaker absworption peak at 260nm.Its infrared spectrum spectrogram (ft-ir) is in 960cm-1Place has one significantly to absorb
Peak.The aperture size in more than 80% hole is more than 2nm.
Comparative example 3,4
Titanium-silicon molecular sieve catalyst as prepared by comparative example 1,2 is carried out catalytic performance by the evaluation methodology of embodiment 7～9 comment
Valency, evaluation result is shown in Table 1.In table 1, the result of comparative example 3,4 corresponds respectively to the HTS as prepared by comparative example 1,2
Catalyst.
Comparative example 5,6
Titanium-silicon molecular sieve catalyst as prepared by comparative example 1,2 is carried out catalytic performance by the evaluation methodology of embodiment 10～12
Evaluate, evaluation result is shown in Table 2.In table 2, the result of comparative example 5,6 corresponds respectively to the titanium silicon molecule as prepared by comparative example 1,2
Sieve catalyst.
Table 1
As can be seen from the above table, the titanium-silicon molecular sieve catalyst of the titanium-silicon molecular sieve catalyst of embodiment 1～3 and comparative example 1 and 2
Compare, its catalyst performance is better than comparative example, ebhp conversion ratio and expoxy propane select equal ＞ 99%.
Table 2
As can be seen from the above table, the titanium-silicon molecular sieve catalyst of the titanium-silicon molecular sieve catalyst of embodiment 4～6 and comparative example 1 and 2
Compare, its catalyst performance is better than comparative example, ebhp conversion ratio and expoxy propane select equal ＞ 99%.
Table 3
As can be seen from the above table, the catalyst performance of the titanium-silicon molecular sieve catalyst of embodiment 1～3 is more excellent, its ebhp conversion ratio
Select equal ＞ 99% with epoxy butane.
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 synthetic method of titanium-silicon molecular sieve catalyst it is characterised in that: described synthetic method comprises the steps:
(1) by silicon source si (or1)4、(r2o)3si-(ch2)n1-si(or3)3(r4)n2si(or5)4-n21/4～4/5 He of total amount
All template [(ch3)3ch3(ch2)n3n+]x-, mineralizer [(ch3cn4h2n4)4nh4]+oh-And water is mixed at normal temperatures
Hydrolysis；
(2) after hydrolysis terminates, by titanium source ti (or6)4It is slowly added under fast stirring after hydrolysis with the mixture of remaining silicon source
Silicon hydroxide solution in, carry out plastic, -5～60 DEG C of gelling temperature；
(3) colloid is transferred to and in crystallizing kettle, carry out crystallization, 100～160 DEG C of crystallization temperature, crystallization time 1～72 hour；
(4) molecular sieve after crystallization is carried out washing, filters and roasting is to remove template, 500～600 DEG C of sintering temperature, roasting
Burn 4～6 hours, obtain final product composite holes titanium-silicon molecular sieve catalyst.
2. titanium-silicon molecular sieve catalyst according to claim 1 synthetic method it is characterised in that: in described step (1)
The silicon source adding accounts for the 1/3～3/4 of silicon source total amount；Gelling temperature in described step (2) is 10～30 DEG C；Described step (3)
In crystallization temperature be 120 DEG C, crystallization time be 12～40 hours；Sintering temperature in described step (4) is 550 DEG C.
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| CN112645345A (en) * | 2020-12-11 | 2021-04-13 | 北京科技大学 | Method for regulating morphology of titanium-silicon molecular sieve based on metal organic framework crystal |
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|---|---|---|---|---|
| CN112645345A (en) * | 2020-12-11 | 2021-04-13 | 北京科技大学 | Method for regulating morphology of titanium-silicon molecular sieve based on metal organic framework crystal |
| CN112645345B (en) * | 2020-12-11 | 2022-04-19 | 北京科技大学 | Method for regulating morphology of titanium-silicon molecular sieve based on metal organic framework crystal |
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Application publication date: 20170125 |