CN108654683A - High stability monoblock type titanium-silicon molecular sieve catalyst and preparation method thereof - Google Patents
High stability monoblock type titanium-silicon molecular sieve catalyst and preparation method thereof Download PDFInfo
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- CN108654683A CN108654683A CN201810335568.7A CN201810335568A CN108654683A CN 108654683 A CN108654683 A CN 108654683A CN 201810335568 A CN201810335568 A CN 201810335568A CN 108654683 A CN108654683 A CN 108654683A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- 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
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- 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
Abstract
The present invention provides a kind of high stability monoblock type titanium-silicon molecular sieve catalysts, are made of active component Titanium Sieve Molecular Sieve and the stainless steel carrier containing certain duct；The Titanium Sieve Molecular Sieve is carried on the stainless steel carrier surface by in-situ crystallization.The present invention also provides the preparation methods of the high stability monoblock type titanium-silicon molecular sieve catalyst.The method of the present invention uses in-situ synthesis, is growing a certain amount of Titanium Sieve Molecular Sieve by surface treatment and on the stainless steel carrier with specific duct, by combining closely for carrier and active component, is achieving the purpose that augmentation of heat transfer.Catalyst prepared by the method for the present invention not only has rate of heat transfer fast, the progress for promoting main reaction in strong exothermal reaction inhibits the generation of side reaction, improves stability, and having many advantages, such as that filling, dismounting are easy, activity component load quantity adjustable range is wide, intensity of load is high.
Description
Technical field
It is the present invention relates to catalyst preparation technical field, more particularly to a kind of to the strongly exothermic oxidation reaction such as alkene epoxidation
The preparation method of monoblock type titanium-silicon molecular sieve catalyst with high stability.
Background technology
Since nineteen eighty-three, since United States Patent (USP) US4410501 reports the synthesis of titanium-silicon molecular sieve TS-1 for the first time, with dioxygen
The reactions such as alkene epoxidation, arene hydroxylation, ketone ammoxidation are shown very high activity by the oxidation system of water composition, and
And by-product is water, belongs to environmentally friendly technology, therefore people is caused widely to pay close attention to.
Thereafter in 30 years, researcher synthesizes the Titanium Sieve Molecular Sieve of a variety of different pore passage structures, makes Titanium Sieve Molecular Sieve
The reaction of different sized molecules is can adapt to, and successively to titanium molecular sieve catalysis phenol hydroxylation preparing benzenediol, cyclohexanone ammonia
The reactions such as oxidation preparing cyclohexanone oxime, butanone ammoxidation diacetylmonoxime and epoxidation of propylene propylene oxide have carried out industrialization and have tasted
Examination, achieves preliminary success.Nevertheless, there are still many to be resolved to ask for titanium molecular sieve catalysis Selective Oxidation
Topic, for example, during epoxidation reaction of olefines catalyst very fast inactivation.
By in epoxidation reaction of olefines, the research of titanium-silicon molecular sieve catalyst deactivation mechanism, people are by catalyst
Inactivation is mainly due to epoxides and solvolysis side reaction occurs with solvent (methanol, water), and the alcohol ethers by-product of generation is easily
With epoxides or its own further polycondensation reaction of generation, dimerization or trimerization alcohol ethers product are generated, relative to titanium silicon point
For the micropore canals size of son sieve, the molecular dimension of this kind of product is larger, to which molecular sieve catalyst can be caused stifled because of duct
It fills in and inactivates.These side reactions are typically considered to carry out on acid site, and therefore, generally use is divided to reaction raw materials or titanium silicon
Micro pK is added in son sieveBThe alkalinity additive (Appl.Catal., A2008,337,58-65) of ＞ 4.5, covers its surface acid
Center inhibits side reaction, and then improves the stability of catalyst, extends its service life.This method is for epoxidation of propylene
Reaction is very effective, can be by one times of catalyst life or more, however, for improving Titanium Sieve Molecular Sieve in butylene, amylene etc.
When stability in the epoxidation reaction of olefines of slightly longer carbochain, party's rule is unsatisfactory.This be primarily due to these compared with
The alcohol ethers by-product size that the alkene of Long carbon chain is generated is slightly longer than molecule with respect to the by-product bigger that propylene generates, length
Channel diameter is sieved, and is more likely formed cyclic side products, thus is easily blocked in duct infall.Alkalinity is added in reactant
Additive can inhibit the generation of alcohol ethers by-product to a certain extent, but very small amount of by-product equally can result in and urge
The serious plug-hole of agent, and then inactivate.Therefore, it is necessary to consider the generation of inhibition alcohol ethers by-product from other angles, improve
The stability of catalyst.
The present invention is, from the angle of Catalyat Engideering, to pass through improvement in the case where not influencing high activity of catalyst
Catalyst heat and mass transfer performance inhibits strongly exothermic to being adversely affected caused by reaction and catalyst stability etc..
Integral catalyzer is by many narrow, parallel channels proper alignment integrated catalyst, and industry for the first time is answered
Be Anderen et al. 1966 with it to the NO in nitric acid workshop tail gasxReduction-decolor.Currently, widely used entirety
Formula carrier includes mainly ceramic honeycomb material (such as cordierite, andalusite) and metal alloy compositions (such as stainless steel, iron containing Al
Ferritic etc.).Vehicle maintenance service uses integral catalyzer, the advantage is that：Bed pressure drop is low, mass-transfer efficiency is high, easy dress
It fills out (single reaction tube only loads a catalyst) and enlarge-effect is small etc., these advantages are adapted to alkene epoxidation etc. and put by force
Thermal response.
Existing seminar has carried out pilot study to integral type T S-1 catalyst both at home and abroad
(Micropor.Mesopor.Mater.1998,21,281-288；Top.Catal.2013,56,182-186；
Chem.Lett.2000,1084-1085；Catal.Today 2004,90,207-213；Appl.Catal.,B 2012,111-
112,67-80；J.Mater.Chem.A2013,1,13821-13827；Catal.Commun.2002,3,221-225), currently,
The preparation of integral type T S-1 catalyst is mostly using cordierite as carrier, preparation method coating or fabricated in situ mainly on carrier
TS-1, before coating or fabricated in situ, usually carrier surface is pre-processed (RSC Adv.2014,4,27259-
27566；Chem.Eng.J.2014,243,192-196), make TS-1 be more easy to grow in carrier surface, rather than in the liquid phase certainly
By growing.However, the thermal conductivity of ceramic material is poor, it is unfavorable for the rapid diffusion of reaction heat, and metal has excellent heat conduction
Property, according to metallic carrier, then it can be obviously improved the heat transfer property of catalyst.
Chinese patent CN102716762 and CN103252253 each provide a kind of using porous silicon carbide as carrier
The active component of integral catalyzer, the catalyst is β, ZSM-5 or Y type molecular sieve, can be obtained containing more using this method
Different size reactants molecules are all had certain catalytic activity by the catalyst of grade pore passage structure.
Invention content
It is an object of the invention to solve in the reaction process such as titanium molecular sieve catalysis alkene epoxidation because of strongly exothermic institute
Caused a series of problems is threatened as caused by thermal accumlation is difficult to diffusion couple safety in production, principal product is selectively low, catalyst
Stability difference etc..
To solve the above problems, present invention offer is a kind of to have high stability to the strongly exothermic oxidation reaction such as alkene epoxidation
Monoblock type titanium-silicon molecular sieve catalyst, the catalyst be by active component Titanium Sieve Molecular Sieve with containing certain duct stainless steel
Carrier forms；The Titanium Sieve Molecular Sieve is carried on the stainless steel carrier surface by in-situ crystallization.Catalyst carrier of the present invention
Reaction heat can be quickly removed, the progress of main reaction is promoted, inhibits side reaction, principal product selectivity is improved, improves simultaneously
The stability of catalyst.
The present invention also provides the preparation method of above-mentioned high stability monoblock type titanium-silicon molecular sieve catalyst, specific steps
For：
S1, Titanium Sieve Molecular Sieve presoma, adhesive, alcohols and deionized water are mixed in proportion, stirs evenly, is glued
Thick shape suspension；
The mass ratio of each substance is in the suspension：
Titanium Sieve Molecular Sieve presoma is (with contained SiO in presoma2Meter):Adhesive:Alcohols:H2O=100:(1.001~
39.999):(10.001~399.999):(10.001~999.999)；
Described adhesive be polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, polymethyl methacrylate,
At least one of polyethyl methacrylate, epoxy resin or polytetrafluoroethylene (PTFE)；
The alcohols is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol or tert-butyl alcohol；
SiO in the Titanium Sieve Molecular Sieve presoma2Content is 1~600g/L；SiO2/TiO2Molar ratio is 5~300；
S2, the suspension for obtaining step S1 move into Rotary Evaporators, 10~60 DEG C of 5~300min of revolving；
S3, molecular sieve in-situ crystallization：The obtained products of step S2 are added dropwise to the stainless steel carrier by surface preparation
In duct, the stainless steel carrier is transferred in crystallizing kettle, 120~200 DEG C of 5~96h of crystallization, by crystallization product 10~
100 DEG C of dryings 1~for 24 hours, then 3~10h is roasted at 500~600 DEG C to get to high stability monoblock type titanium molecular sieve catalysis
Agent；
The stainless steel carrier is cylinder, and diameter of section is 6~80mm, is highly 1~500cm, carrier inside is
With the netted pore passage structure of stainless (steel) wire filling waviness, porosity is 5~100 mesh, material SUS304, SUS304L,
One kind in SUS316, SUS316L；
It is described to stainless steel carrier carry out surface preparation include：Acid processing and curing agent coating processing；
The acid handles concrete operations：Stainless steel carrier is immersed in 1 in concentrated acid solution at 5~80 DEG C~for 24 hours, it takes
Go out to be washed till neutrality, dry 10 at 80~100 DEG C~for 24 hours；
The curing agent coating processing concrete operations are：Curing agent is added dropwise in the stainless steel carrier duct through peracid treatment
Aqueous solution, then carrier is put into centrifuge 1~10min of centrifugation under the rotating speed of 10~200r/min；
The curing agent be diethylenetriamine, triethylene tetramine, tetraethylenepentamine, dipropylenetriamine, dimethylamine propylamine,
At least one of diethyl amino propylamine, ethylenediamine tetra-acetic acid；A concentration of 1~the 300g/L of aqueous solution of curing agent.
Under preferred embodiment, Titanium Sieve Molecular Sieve described in step S1 is in micropore, mesoporous or Jie's micropore compound titanium silicon molecular sieve
It is a kind of；It advanced optimizes, is one kind in TS-1, TS-2, Ti-MWW, Ti- β, Ti-TUD-1 molecular sieve.
Under optimal situation, the preparation method of Titanium Sieve Molecular Sieve described in step S1 is：By silicon source, titanium source, template and alkali source
0.5~8h is mixed or hydrolyzed respectively at 20~60 DEG C, then mixing removes 0~10h of alcohol at 60~95 DEG C；The preferably positive silicic acid of the silicon source
At least one of methyl esters, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, Ludox, white carbon；The preferred metatitanic acid of titanium source
In tetra-ethyl ester, metatitanic acid orthocarbonate, butyl titanate, titanium trichloride, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanyl nitrate extremely
Few one kind；Alkali source is at least one of methylamine, ethamine, propylamine, diethylamine, ethylenediamine, quaternary ammonium base organic base, or is ammonia
At least one of water, sodium hydroxide, potassium hydroxide inorganic base.
Wherein, when the Titanium Sieve Molecular Sieve is TS-1 molecular sieves, the preferred tetrapropylammonium hydroxide of template, tetrapropyl bromine
Change at least one of ammonium；
When the Titanium Sieve Molecular Sieve is TS-2 molecular sieves, the preferred tetrabutylammonium hydroxide of template, tetrabutylammonium bromide
At least one of；
When the Titanium Sieve Molecular Sieve is Ti-MWW molecular sieves, boron source and Fluorine source need to be added；The preferred hexa-methylene of template
At least one of secondary amine, tetramethylammonium hydroxide, piperidines；Fluorine source is hydrofluoric acid；Boron source is boric acid；
When the Titanium Sieve Molecular Sieve is Ti- beta-molecular sieves, the preferred tetraethyl ammonium hydroxide of template, tetraethylammonium bromide
At least one of；
When the Titanium Sieve Molecular Sieve is Ti-TUD-1 molecular sieves, the preferred triethanolamine of template.
For in above-mentioned molecular sieve, the molar ratio of each raw material is silicon source in TS-1, TS-2 and Ti- beta-molecular sieve presoma:Titanium
Source:Template:Water=1:(0.001~0.0699):(0.025~0.599):(2.001~65.999)；Before Ti-MWW molecular sieves
The molar ratio for driving each raw material in body is silicon source:Titanium source:Template:Fluorine source:Boron source:Water=1:(0.001~0.0499):(0.025
~2.599):(0.101~1.999):(0.501~1.999):(7.001~64.999)；In Ti-TUD-1 molecular sieve precursors
The molar ratio of each raw material is silicon source:Titanium source:Template:Water=1:(0.001~0.0499):(0.025~0.999):(5.001
~76.999).
Under preferred embodiment, step S3 molecular sieve in-situ crystallizations repetitive operation 0~10 time, with adjust molecular sieve layer load capacity and
Thickness；Load capacity ranging from every gram of carrier loaded 0.01~5g molecular sieve；Load thickness is 0.1~10mm.
Under preferred embodiment, the acid that acid processing uses described in step S3 is 40% hydrofluoric acid of mass fraction or mass fraction 40%
One kind in salpeter solution.
The synthetic method of Titanium Sieve Molecular Sieve provided in the present invention has the following advantages compared with prior art：
1. heat transfer efficiency is high, rate of heat transfer is fast, can promote the progress of main reaction in epoxidation reaction of olefines, inhibits secondary anti-
The generation answered improves principal product selectivity, improves the stability of catalyst.
2. integral catalyzer have the advantages that filling, dismantle it is simple, and catalyst size can pass through adjust carrier ruler
It is very little and change, to be suitable for various sizes of reactor.
3. catalyst loadings can be in regulated in wider range, to adapt to differential responses.
4. integral catalyzer and active component are high in the intensity of supported on carriers, after reaction repeatedly, active component retains
Rate>98%.
To sum up, the present invention provides a kind of monoblock types to the strongly exothermic oxidation reaction such as alkene epoxidation with high stability
The preparation method of titanium-silicon molecular sieve catalyst, which is characterized in that the catalyst is by active component Titanium Sieve Molecular Sieve and stainless steel
Carrier forms, and carrier can quickly remove reaction heat, promote the progress of main reaction, inhibits side reaction, improves epoxidation
Object selectivity, while improving the stability of catalyst.
Description of the drawings
Fig. 1 is the photo of integral catalyzer TS-MA and TS-MF.
Fig. 2 is each catalyst propylene ring oxidation reaction performance in application examples 1, as seen from the figure, identical active component
The stability of integral catalyzer is above extruded moulding catalyst.
Fig. 3 is each catalyst 1- butylene epoxidation reaction performance in application examples 2, as seen from the figure, identical active component
The stability of integral catalyzer be above extruded moulding catalyst.
Specific implementation mode
Comparative example 1
TS-1 molecular sieves are prepared according to the method that Chinese patent CN1401569 is provided：355g ethyl orthosilicates are added three
In mouth flask, 319.5g tetrapropylammonium hydroxide solutions and 284g water are added under 25 DEG C, magnetic agitation, makes ethyl orthosilicate
Hydrolyze 90min；106.5g isopropanols are added in 14.2g butyl titanates, 120.7g tetrapropyl hydrogen is sequentially added under stirring
Ammonium hydroxide solution and 142g water, hydrolyze 30min at room temperature, obtain tetrabutyl titanate hydrolysis object.By estersil and titanium esters hydrolysate
Mixing, and at 85 DEG C remove alcohol 6h, obtained clear solution TS-LA is fitted into crystallizing kettle, at 170 DEG C crystallization for 24 hours, crystallization
Product is washed, it is dry after, 5h is roasted at 540 DEG C, TS-1 powder is obtained, is denoted as TS-PA.
The method provided using embodiment 6 in Chinese patent CN103464197 by above-mentioned TS-PA powder extruded moulding,
And the particle of 1mm × 2mm is cut into, molding TS-1 catalyst is obtained, TS-EA is denoted as.
Comparative example 2
TS-2 molecular sieves are prepared according to the method that document (Appl.Catal.1990,58, L1-L4) provides：By the positive silicon of 45g
After acetoacetic ester, 25g isopropanols and the mixing of 25g deionized waters, it is added in three-necked flask, is slow added into the tetrabutyl of 10g 40%
Ammonium hydroxide aqueous solution；Under agitation, 1.13g butyl titanates are added drop-wise in 10g isopropanols, then metatitanic acid four will be obtained
Butyl ester alcoholysate is added in three-necked flask, stirs 1h at 57 DEG C, makes esters complete hydrolysis, and forms transparency liquid mixture.
Finally, it after the tetrabutylammonium hydroxide aqueous solution of 40g 40% being mixed with 70g deionized waters, is added in above-mentioned three-necked flask,
It stirs evenly, alcohol 8h is removed at 80 DEG C.Obtained clear solution TS-LB is fitted into crystallizing kettle, the crystallization 8d at 170 DEG C, it is brilliant
Change product it is washed, it is dry after, 5h is roasted at 540 DEG C, TS-2 powder is obtained, is denoted as TS-PB.
The method provided using embodiment 6 in Chinese patent CN103464197 by above-mentioned TS-PB powder extruded moulding,
And the particle of 1mm × 2mm is cut into, molding TS-2 catalyst is obtained, TS-EB is denoted as.
Comparative example 3
Ti-MWW molecular sieves are prepared according to the method that embodiment 1 is provided in Chinese patent CN1321061：By 119g piperidines
It after being mixed with 172g deionized waters, is added in three-necked flask, then 11.2g butyl titanates are added in piperidine solution, stirs
Uniformly, 41.4g boric acid and 40% hydrofluoric acid of 20g is added, stirs evenly, is eventually adding 30% Ludox of 200g；By what is obtained
Mixture TS-LC crystallization 7d at 170 DEG C, crystallization product is washed, it is dry after, obtain Ti-MWW original powders；By this original powder of 50g with
The salpeter solution of a concentration of 2mol/L of 2.5kg mixes, and handles 20h at 100 DEG C, using being filtered, washed, drying, obtains acid
Handle product；10h is roasted at 550 DEG C, is obtained Ti-MWW powder, is denoted as TS-PC.
The method provided using embodiment 6 in Chinese patent CN103464197 by above-mentioned TS-PC powder extruded moulding,
And the particle of 1mm × 2mm is cut into, molding Ti-MWW catalyst is obtained, TS-EC is denoted as.
Comparative example 4
According to document (J.Mol.Catal.A:Chem.2010,328,60-67) method provided prepares Ti- beta-molecular sieves：
8.5g butyl titanates are mixed with 30% aqueous hydrogen peroxide solutions of 38g in three-necked flask, peroxo complexes are formed；
Under strong stirring, the tetraethyl ammonium hydroxide aqueous solution of 202.5g 40% is sequentially added, 30% Ludox of 200g and 1.8g divide
Son sieve crystal seed, stirs 30min；Obtained homogeneous gel TS-LD is fitted into crystallizing kettle, crystallization 5d, crystallization product at 140 DEG C
After washed, dry, 12h is roasted at 520 DEG C, Ti- β powder is obtained, is denoted as TS-PD.
The method provided using embodiment 6 in Chinese patent CN103464197 by above-mentioned TS-PD powder extruded moulding,
And the particle of 1mm × 2mm is cut into, molding Ti- beta catalysts are obtained, TS-ED is denoted as.
Following non-limiting embodiments can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
The specific method of the present invention includes the following steps：
S1, Titanium Sieve Molecular Sieve presoma, adhesive, alcohols and deionized water are mixed in proportion, stirs evenly, obtains
Thick suspension；
S2, the obtained suspensions of step S1 are placed in Rotary Evaporators, 5~300min is handled at 10~60 DEG C；
S3, the product for obtaining step S2 are coated on the stainless steel carrier Jing Guo surface preparation, are done at 10~100 DEG C
Dry 1~for 24 hours, 3~10h is roasted at 500~600 DEG C to get to monoblock type titanium-silicon molecular sieve catalyst.
Embodiment 1
It using diameter of section for 15mm, is highly 10cm, porosity is 40 mesh, and material is the stainless steel carrier of SUS316L,
At 25 DEG C, it is washed with deionized for 24 hours, after taking-up to neutrality using 40% hydrofluoric acid dips carrier；At 25 DEG C, to carrier
Duct in the triethylene tetramine solution of a concentration of 50g/L is added dropwise, make to be filled by triethylene tetramine in each duct, carrier put
Enter in centrifuge, 2min is centrifuged with the rotating speed of 100r/min, takes out carrier；The 33g clear solutions TS- that will be prepared in comparative example 1
LA is mixed with 1.5g polymethyl acrylate, 10g ethyl alcohol and 27g water, is stirred evenly, and in 40 DEG C of rotary evaporation 30min, is obtained sticky
Shape suspension is added dropwise in above-mentioned treated carrier duct, 80 DEG C of oven drying 12h is put into, at 540 DEG C after taking-up
5h is roasted, integral type T S-1 catalyst is obtained, is denoted as TS-MA.Molecular sieve layer thickness is 0.05mm.Fig. 1 urges for monoblock type
The photo of agent TS-MA and TS-MF.
Embodiment 2
Solution TS-LA in embodiment 1 is changed to by TS-LB obtained in comparative example 2, other steps and 1 phase of embodiment
Together, the integral type T S-2 catalyst obtained, is denoted as TS-MB.Molecular sieve layer thickness is 0.05mm.
Embodiment 3
Solution TS-LA powder in embodiment 1 is changed to by TS-LC obtained in comparative example 3, other steps and embodiment
1 is identical, and obtained integral type T i-MWW catalyst is denoted as TS-MC.Molecular sieve layer thickness is 0.05mm.
Embodiment 4
It using diameter of section for 40mm, is highly 20cm, porosity is 20 mesh, and material is the stainless steel carrier of SUS304,
At 25 DEG C, it is washed with deionized for 24 hours, after taking-up to neutrality using 40% nitric acid dousing carrier；At 25 DEG C, to carrier
Ethylenediamine tetra-acetic acid is added dropwise in duct, makes to be filled by ethylenediamine tetra-acetic acid in each duct, carrier is put into centrifuge, with
The rotating speed of 50r/min centrifuges 3min, takes out carrier；By the 45g clear solutions TS-LA prepared in comparative example 1 and the poly- methyl of 1.5g
Ethyl acrylate, 18g methanol and 70g water are uniformly mixed, and in 40 DEG C of rotary evaporation 60min, are obtained thick suspension, are dripped
It is added in treated carrier duct, is put into 80 DEG C of oven drying 12h, roast 5h after taking-up at 540 DEG C, obtain monoblock type
TS-1 catalyst, is denoted as TS-MD.Molecular sieve layer thickness is 0.10mm.
Embodiment 5
Solution TS-LA in embodiment 4 is changed to by TS-LD obtained in comparative example 4, other steps and 4 phase of embodiment
Together, the integral type T i- beta-molecular sieves obtained, are denoted as TS-ME.Molecular sieve layer thickness is 0.10mm.
Embodiment 6
It using diameter of section for 15mm, is highly 10cm, porosity is 10 mesh, and material is the stainless steel carrier of SUS316,
At 25 DEG C, it is washed with deionized for 24 hours, after taking-up to neutrality using 40% hydrofluoric acid dips carrier；At 25 DEG C, to carrier
Duct in the diethylenetriamine solution of a concentration of 35g/L is added dropwise, make to be filled by edta solution in each duct, will
Carrier is put into centrifuge, is centrifuged 1min with the rotating speed of 80r/min, is taken out carrier；The 33g prepared in comparative example 1 is clarified molten
Liquid TS-LA is uniformly mixed with 3g epoxy resin and the 35g tert-butyl alcohols, in 30 DEG C of rotary evaporation 120min, obtains thick suspension,
It is added dropwise in treated carrier duct, is put into 80 DEG C of oven drying 12h, 5h is roasted after taking-up at 540 DEG C, in repetition
Fabricated in situ step 4 time is stated, integral type T S-1 catalyst is obtained, is denoted as TS-MF.Molecular sieve layer thickness is 0.5mm.Fig. 1
For the photo of integral catalyzer TS-MA and TS-MF.
Application examples 1
The monoblock type titanium-silicon molecular sieve catalyst prepared in above-mentioned comparative example and embodiment is used for fixed bed reactors
Propylene liquid phase epoxidation reaction, reaction condition is as follows：Loaded catalyst 5g (in terms of active component), 40 DEG C, 3.0MPa,
35wt%H2O2Solution feed amount 4.9mL/h, methanol inlet amount 13.6mL/h, propylene feed amount 14.3mL/h take out every 12h
Product is analyzed, using iodometric titrationiodimetry titration H2O2Concentration, gas chromatographic analysis product assay, the results are shown in Figure 2.
Note：X(H2O2) indicate H2O2Conversion ratio, by formula (1) calculate：
X(H2O2- n (the H of)=12O2)/n0(H2O2) (1)
In formula, n0(H2O2) and n (H2O2) the front and back H of reaction is indicated respectively2O2Substance withdrawl syndrome.
Application examples 2
The monoblock type titanium-silicon molecular sieve catalyst prepared in above-mentioned comparative example and embodiment is used for fixed bed reactors
1- butylene liquid phase epoxidation reactions, reaction condition is as follows：Loaded catalyst 5g (in terms of active component), 40 DEG C, 3.0MPa,
35wt%H2O2Solution feed amount 2.5mL/h, methanol inlet amount 16.1mL/h, 1- butene feed amount 7.0mL/h take out every 12h
Product is analyzed, using iodometric titrationiodimetry titration H2O2Concentration, gas chromatographic analysis product assay, the results are shown in Figure 3.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of high stability monoblock type titanium-silicon molecular sieve catalyst, which is characterized in that by active component Titanium Sieve Molecular Sieve with contain
It is made of the stainless steel carrier in certain duct；The Titanium Sieve Molecular Sieve is carried on the stainless steel carrier table by fabricated in situ
Face.
2. the preparation method of high stability monoblock type titanium-silicon molecular sieve catalyst described in claim 1, which is characterized in that specific system
It is standby that steps are as follows：
S1, Titanium Sieve Molecular Sieve presoma, adhesive, alcohols and deionized water are mixed in proportion, is stirred evenly, obtained thick
Suspension；
The mass ratio of each substance is in the suspension：
Titanium Sieve Molecular Sieve presoma is (with contained SiO in presoma2Meter):Adhesive:Alcohols:H2O=100:(1.001~
39.999):(10.001~399.999):(10.001~999.999)；
SiO in the Titanium Sieve Molecular Sieve presoma2Content is 1~600g/L；SiO2/TiO2Molar ratio is 5~300；
Described adhesive is polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, polymethyl methacrylate, poly- first
At least one of base ethyl acrylate, epoxy resin or polytetrafluoroethylene (PTFE)；
The alcohols is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol or tert-butyl alcohol；
S2, the suspension for obtaining step S1 move into Rotary Evaporators, 10~60 DEG C of 5~300min of revolving；
S3, molecular sieve in-situ crystallization：The obtained products of step S2 are added dropwise to the stainless steel carrier duct by surface preparation
It is interior, the stainless steel carrier is transferred in crystallizing kettle, 120~200 DEG C of 5~96h of crystallization, by crystallization product at 10~100 DEG C
Dry 1~for 24 hours, then 3~10h is roasted at 500~600 DEG C to get to high stability monoblock type titanium-silicon molecular sieve catalyst；
The stainless steel carrier is cylinder, and diameter of section is 6~80mm, is highly 1~500cm, and carrier inside is with not
The netted pore passage structure of steel mesh filling waviness of becoming rusty, porosity are 5~100 mesh, material SUS304, SUS304L,
One kind in SUS316, SUS316L；
It is described to stainless steel carrier carry out surface preparation include：Acid processing and curing agent coating processing；
The acid handles concrete operations：Stainless steel carrier is immersed in 1 in concentrated acid solution at 5~80 DEG C~for 24 hours, taking-up is washed
To neutrality, dry 10 at 80~100 DEG C~for 24 hours；
The curing agent coating processing concrete operations are：It is water-soluble that curing agent is added dropwise in the stainless steel carrier duct through peracid treatment
Liquid, then carrier is put into centrifuge 1~10min of centrifugation under the rotating speed of 10~200r/min；
The curing agent is diethylenetriamine, triethylene tetramine, tetraethylenepentamine, dipropylenetriamine, dimethylamine propylamine, diethyl
At least one of amido propylamine, ethylenediamine tetra-acetic acid；A concentration of 1~the 300g/L of aqueous solution of curing agent.
3. the preparation method of high stability monoblock type titanium-silicon molecular sieve catalyst according to claim 2, which is characterized in that step
Titanium Sieve Molecular Sieve described in rapid S1 is one kind in micropore, mesoporous or Jie's micropore compound titanium silicon molecular sieve.
4. the preparation method of high stability monoblock type titanium-silicon molecular sieve catalyst according to claim 3, which is characterized in that be
One kind in TS-1, TS-2, Ti-MWW, Ti- β, Ti-TUD-1 molecular sieve.
5. the preparation method of high stability monoblock type titanium-silicon molecular sieve catalyst according to claim 2, which is characterized in that step
Rapid S3 molecular sieve in-situ crystallizations repetitive operation 0~10 time, to adjust molecular sieve layer load capacity and thickness；Ranging from every gram of load capacity
Carrier loaded 0.01~5g molecular sieves；Load thickness is 0.1~10mm.
6. the preparation method of high stability monoblock type titanium-silicon molecular sieve catalyst according to claim 2, which is characterized in that step
The acid that acid processing uses described in rapid S3 is at least one of 40% salpeter solution of 40% hydrofluoric acid of mass fraction or mass fraction.
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