CN104528758B - A kind of post-processing approach of 1 HTSs of TS - Google Patents
A kind of post-processing approach of 1 HTSs of TS Download PDFInfo
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- CN104528758B CN104528758B CN201410811161.9A CN201410811161A CN104528758B CN 104528758 B CN104528758 B CN 104528758B CN 201410811161 A CN201410811161 A CN 201410811161A CN 104528758 B CN104528758 B CN 104528758B
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Abstract
The invention provides a kind of 1 HTS post-processing approachs of TS, process is modified to 1 HTSs of TS using the mixed solution of a kind of strong acid and Fluohydric acid., the extra-framework titanium in molecular sieve system can effectively be removed, the surface texture of molecular sieve is improved, modified 1 HTSs of TS have more preferable catalysis activity and catalytic life.
Description
Technical field
The invention belongs to petrochemical industry catalysis technical field, and in particular to a kind of that there is MFI structure TS-1 HTS
Post-processing approach.
Background technology
TS-1 HTSs are that transition metal titanium is introduced into formed in the framework of molecular sieve with MFI structure
Plant the novel titanosilicate with excellent selective paraffin oxidation catalytic performance.It not only has the catalysed oxidn of titanium, and has
Have the shape-selective effect of MFI and excellent stability, with excellent oxidisability and specific selectivity, can be widely applied to benzene,
In the oxidation reaction of the Organic substances such as phenol, alcohols, ethers.Cyclohexanone oxamidinating and epoxidation of propylene etc. have been carried out industry at present
Metaplasia is produced, in addition the green catalysis system of TS-1 HTSs and hydrogen peroxide composition, it is to avoid complex process and pollution environment
Problem, it may have good prospects for commercial application.
1981, USP4410501 made public for the first time TS-1's and into method, through continuous development and the research of 40 years, mesh
The Hydrothermal Synthesiss of front TS-1 have formed two kinds of systems, and one kind is to do template synthesis using TPAOH (TPAOH)
HTS, referred to as classical formalism, another kind are to be template synthesis TS-1 using cheap 4-propyl bromide, are claimed
For cheap system, in addition with various methods such as isomorphous substitution.But Ti-O keys are because compared with Si-O bond distance, titanium atom enters skeleton
The TS-1 of relatively difficult therefore current synthetic method synthesis can produce extra-framework titanium, and TS-1 is had a negative impact.It is first
First extra-framework titanium itself does not have catalytic oxidation activity but can cause a large amount of decomposition of hydrogen peroxide, thus causes TS-1 catalytics
The reduction of energy；Secondly, the content of extra-framework titanium is unmanageable, and this causes the activity stability of HTS poor, so
Constrain the commercial Application of TS-1.
In order to extra-framework titanium be reduced to lift the performance of molecular sieve, many researchs being modified for TS-1 at present, mainly
Hole is produced in TS-1 using inorganic base or being modified for organic base, promotes the diffusion of reactant and product, this method is often
Need through secondary crystallization process, be easily caused the secondary of TS-1 particles for having prepared and grow up, be unfavorable for that TS-1 particle diameters are had
Effect control.
The content of the invention
The invention provides a kind of new TS-1 HTS post-processing approachs, using joint acid treatment process pair
TS-1 is modified, and effectively improves catalytic performance and the life-span of TS-1.
The technical scheme that the invention is adopted is, using the mixed solution of a kind of strong acid and Fluohydric acid. to TS-1 titaniums silicon point
Son sieve is modified process.
Further, the technical scheme that the invention is adopted is, with every gram of TS-1 HTSs correspondence 2-25ml strong acid
With the ratio of the mixed solution of Fluohydric acid., process is modified to TS-1 HTSs, wherein, the strong acid and Fluohydric acid.
In mixed solution, the H of strong acid+Concentration is 0.0025～0.05mol/L, and the mass fraction of Fluohydric acid. is 0.005～0.15%.
Further, the strong acid be hydrochloric acid, sulphuric acid, one or more in nitric acid.
Further, the post-processing approach that the invention is provided also is included TS-1 HTSs and above-mentioned strong acid and hydrogen
The mixed solution of fluoric acid is under agitation the step of reacting for 25-100 DEG C.
Further, the post-processing approach that the invention is provided also include TS-1 HTSs and above-mentioned strong acid and
The step of mixed solution of Fluohydric acid. reacts 2-6h under the rotating speed of 50-100r/min at 25-100 DEG C, in being washed till after reaction
Property.Course of reaction can carry out one or many, preferably 2-3 time.
By the TS-1 HTSs drying after the completion of the mixed solution reaction with strong acid and Fluohydric acid., in 500-650 DEG C
Lower roasting 3-6h, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
The invention is modified to TS-1 HTSs using the joint acid treatment process of strong acid and Fluohydric acid., energy
Enough extra-framework titaniums effectively removed in molecular sieve system, improve the surface texture of molecular sieve, and modified technique is simple, easy to operate,
Avoid the impact to molecular sieve structure because of secondary crystallization process so that modified TS-1 HTSs have preferably urges
Change activity and catalytic life.
Specific embodiment
The invention is further described below by specific embodiment.Following examples are only to illustrate the invention
Purpose rather than limit, in embodiment and comparative example, NM process conditions or process are according to conventional process conditions or parameter
Carry out.
Embodiment 1
It is 0.01mol/L that concentrated sulphuric acid addition deionized water is diluted to H+ concentration, and Fluohydric acid. is added deionized water dilution
It is 0.01% to mass fraction, then by both solution with standby after the mixing of volume ratio 1: 1.
Weigh 40g TS-1 titanium-silicon molecular sieve catalysts to be put in the reactor of politef or polypropylene material, measure
The mixed solution 200ml for taking the strong acid and Fluohydric acid. for preparing is poured in reactor, opens stirring, and rotating speed is 50r/min, in 25 DEG C
Stop stirring after lower reaction 2h, neutrality is washed till with deionized water.This process is repeated into 3 times.Reaction completes post-drying, in
Roasting 3h at 500 DEG C, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
Embodiment 2
Concentrated hydrochloric acid addition deionized water is diluted to into H+Concentration is 0.1mol/L, and Fluohydric acid. addition deionized water is diluted to
Mass fraction is 0.2%, then by both solution with standby after the mixing of volume ratio 1: 3.
Weigh 100g TS-1 titanium-silicon molecular sieve catalysts to be put in the reactor of politef or polypropylene material,
The mixed solution 1000ml for measuring the strong acid and Fluohydric acid. for preparing is poured in reactor, opens stirring, and rotating speed is 100r/min, in
Stop stirring after 6h is reacted at 100 DEG C, neutrality is washed till with deionized water.This process is repeated into 3 times.Reaction completes after bake
It is dry, the roasting 6h at 650 DEG C, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
Embodiment 3
Concentrated nitric acid addition deionized water is diluted to into H+Concentration is 0.05mol/l, and Fluohydric acid. is added deionized water dilution
It is 0.15% to mass fraction, then by both solution with standby after the mixing of volume ratio 1: 2.
Weigh 60g TS-1 titanium-silicon molecular sieve catalysts to be put in the reactor of politef or polypropylene material, measure
The mixed solution 500ml for taking the strong acid and Fluohydric acid. for preparing is poured in reactor, opens stirring, and rotating speed is 70r/min, in 80 DEG C
Stop stirring after lower reaction 4h, neutrality is washed till with deionized water.This process is repeated into 3 times.Reaction completes post-drying, in
Roasting 4h at 550 DEG C, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
Comparative example 1
Concentrated hydrochloric acid addition deionized water is diluted to into H+Concentration is standby after 0.05mol/l.
Weigh 60g TS-1 titanium-silicon molecular sieve catalysts to be put in the reactor of politef or polypropylene material, measure
The mixed solution 500ml for taking the strong acid and Fluohydric acid. for preparing is poured in reactor, opens stirring, and rotating speed is 70r/min, in 80 DEG C
Stop stirring after lower reaction 4h, neutrality is washed till with deionized water.This process is repeated into 3 times.Reaction completes post-drying, in
Roasting 4h at 550 DEG C, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
Comparative example 2
Fluohydric acid. addition deionized water is diluted to into mass fraction for standby after 0.15%.
Weigh 60g TS-1 titanium-silicon molecular sieve catalysts to be put in the reactor of politef or polypropylene material, measure
The mixed solution 500ml for taking the strong acid and Fluohydric acid. for preparing is poured in reactor, opens stirring, and rotating speed is 70r/min, in 80 DEG C
Stop stirring after lower reaction 4h, neutrality is washed till with deionized water.This process is repeated into 3 times.Reaction completes post-drying, in
Roasting 4h at 550 DEG C, you can obtain TS-1 titanium-silicon molecular sieve catalyst products.
Comparative example 3
The TS-1 titanium-silicon molecular sieve catalysts prepared using same method, but without aftertreatment technology step.
Above-described embodiment and comparative example are obtained HTS product to be evaluated during following：Ketohexamethylene amidoxime
Changing reaction is carried out on the continuous slurry-bed reaction device of normal pressure, and wherein molecular sieve is separated with liquid reaction mixture and adopts aperture
Ceramic membrane for 100nm is completed, and loaded catalyst is 50g, and in raw material, Ketohexamethylene, hydrogen peroxide, ammonia are mixed with certain proportion
Form, solvent is done with the tert-butyl alcohol, reaction temperature is 70～90 DEG C, and sampling, uses gas chromatographic analysiss product, obtain Ketohexamethylene per 2h
Conversion ratio and Ketohexamethylene selectivity, when conversion ratio be less than 90% when judges catalyst as inactivate.Evaluation result such as 1 institute of table
Show.
1 different embodiment institute modified catalyst cyclohexanone oxamidinating evaluation results of table
| Catalyst life/h | Ketohexamethylene average conversion/% | Cyclohexanone-oxime average selectivity/% | |
| Embodiment 1 | 70 | 93.2 | 93.6 |
| Embodiment 2 | 90 | 93.7 | 94.8 |
| Embodiment 3 | 240 | 97.9 | 99.7 |
| Comparative example 1 | 60 | 90.4 | 92.5 |
| Comparative example 2 | 70 | 90.3 | 91.1 |
| Comparative example 3 | 60 | 91.4 | 91.3 |
Claims (3)
1. a kind of TS-1 HTSs post-processing approach, corresponds to 2-25ml strong acid and hydrogen including with every gram of TS-1 HTS
The ratio of the mixed solution of fluoric acid, the step of be modified process to TS-1 HTSs, wherein, the strong acid and Fluohydric acid.
Mixed solution in, the H of strong acid+Concentration is 0.0025～0.05mol/L, and the mass fraction of Fluohydric acid. is 0.005～0.15%；
The strong acid is hydrochloric acid, sulphuric acid, one or more in nitric acid；
Also include by the mixed solution of TS-1 HTSs and the strong acid and Fluohydric acid. under the rotating speed of 50-100r/min in
The step of reacting 2-6h at 25-100 DEG C, is washed till neutrality after reaction；Course of reaction carries out one or many.
2. a kind of TS-1 HTSs post-processing approach according to claim 1, it is characterised in that：Course of reaction is carried out
2-3 time.
3. a kind of TS-1 HTSs post-processing approach according to claim 1, it is characterised in that：Will be with the strong acid
With the TS-1 HTSs drying after the completion of the mixed solution reaction of Fluohydric acid., the roasting 3-6h at 500-650 DEG C, you can
TS-1 titanium-silicon molecular sieve catalyst products.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN101148260A (en) * | 2007-08-20 | 2008-03-26 | 华东师范大学 | Titanium-silicon molecular screen with MWW structure and its synthesis and application |
| CN103708494A (en) * | 2013-12-26 | 2014-04-09 | 中国天辰工程有限公司 | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN101148260A (en) * | 2007-08-20 | 2008-03-26 | 华东师范大学 | Titanium-silicon molecular screen with MWW structure and its synthesis and application |
| CN103708494A (en) * | 2013-12-26 | 2014-04-09 | 中国天辰工程有限公司 | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve |
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