CN105749966A - Cyclic regeneration method of Ti-HSZ (Ti-containing hollownest-structured zeolite) catalyst - Google Patents
Cyclic regeneration method of Ti-HSZ (Ti-containing hollownest-structured zeolite) catalyst Download PDFInfo
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- CN105749966A CN105749966A CN201610139189.1A CN201610139189A CN105749966A CN 105749966 A CN105749966 A CN 105749966A CN 201610139189 A CN201610139189 A CN 201610139189A CN 105749966 A CN105749966 A CN 105749966A
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- catalyst
- hsz
- aqueous solution
- regeneration method
- ethanol
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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
- B01J29/90—Regeneration or reactivation
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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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
-
- 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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a cyclic regeneration method of a Ti-HSZ (Ti-containing hollownest-structured zeolite) catalyst.The cyclic regeneration method includes the steps of 1), recycling the Ti-HSZ catalyst subjected to olefin epoxidation reaction, filtering and drying for standby use; 2), mixing the recycled Ti-HSZ catalyst with a regeneration solution in a mass ratio of 1:50-70, stirring at 25-85 DEG C for 2-36 hours, filtering and drying so as to obtain regenerated Ti-HSZ catalyst.The recycled Ti-HSZ catalyst is treated by a mixed solution of H2O2 aqueous solution and ethyl alcohol according to a specific mixing ratio and then is filtered and dried so as to be regenerated, and accordingly the cyclic regeneration method requires no high-temperature roasting treatment, is high in safety and short in regeneration time, good in cyclic regeneration effect and high in stability and can be recycled for multiple times.
Description
Technical field
The present invention relates to the technical field of titanium-containing molecular sieve catalyst renovation process, in particular to one
Plant the circulation regeneration method of Ti-HSZ catalyst.
Background technology
Molecular sieve containing titanium is maximally effective catalyst in EPOXIDATION OF ALKENES CATALYZED BY, but its
Catalyzing expoxidation of olefines experiment is prone to lose activity, is used for multiple times containing titanium molecule to be able to circulation
Sieve needs it is carried out Regeneration Treatment.In prior art, CN 102513152A is first by inactivation
HTS is mixed homogeneously with a kind of regeneration colloid, then steams through saturation water in sealing container
Process under the conditions of gas, then drying, roasting obtain regenerating HTS.EP0100119 adopts
With molecular sieve containing titanium epoxidation of propylene with the method preparing expoxy propane, the regeneration side wherein proposed
Formula has 550 DEG C of high-temperature roastings, and the solvent washing that methanol or course of reaction use.
USP6878836B2 discloses a kind of employing methanol high-temperature wash regeneration method, and the method is
By the wash temperatures of more than 100 DEG C, decaying catalyst is carried out methanol washing.CN104119215
A discloses a kind of regenerating molecular sieve method in acetone continuous dehydration production technology, preferably adds
Hot temperature 170～200 DEG C, heat time heating time 1～3 hours.It follows that at present for titaniferous
The regeneration of molecular sieve is main by the method for high-temperature calcination, or is cleaned and high-temperature calcination by acetone
Combine, be required to high-temperature calcination and process.If the method cleaned only with acetone, catalyst
After recycling four times, the conversion ratio of chlorine propylene greatly reduces, and acetone has been listed in easily system
Poison reagent, purchases program complicated.
Molecular sieve hollow sphere is the important member in grading-hole molecular sieves, has micropore-big
Hole composite construction.Wherein, Ti-HSZ (Ti-containing hollownest-structured zeolite,
Titaniferous hollow Nest architecture molecular sieve) catalyst has high external surface area, the shell wall of this catalyst
Being made up of nanoscale twins Ti-MWW crystal, inside is distinctive hollow Nest architecture.At present,
Circular regeneration side for titaniferous hollow Nest architecture molecular sieve (Ti-HSZ) catalyst not yet occurs
Method.
Summary of the invention
Present invention aim to provide the circulation regeneration method of a kind of Ti-HSZ catalyst,
Due to the special construction feature of Ti-HSZ catalyst, by using the H of certain proportioning2O2Water-soluble
The mixed liquor of liquid and the ethanol Ti-HSZ catalyst treatment to reclaiming, can wash off to remain in and urge
Substrate molecule in agent, then catalyst can be made to regenerate, not only without height through filtering, being dried
Temperature calcination processing, security performance is high, the recovery time is short, and catalytic regeneration is effective, stably
Property high, can be recycled for multiple times.
For achieving the above object, the circulation of a kind of Ti-HSZ catalyst provided by the present invention is again
Generation method, after being reclaimed by the Ti-HSZ catalyst after epoxidation reaction of olefines, utilizes H2O2
The mixed liquor cleaning and regeneration of aqueous solution and ethanol.
Further, described mixed liquor is by H2O2Aqueous solution and ethanol be in mass ratio 1:1～
10 is formulated.
Preferably, described mixed liquor is by H2O2Aqueous solution and ethanol are in mass ratio
1:2～8 formulated.
Most preferably, described mixed liquor is by H2O2Aqueous solution and ethanol are 1:4～6 in mass ratio
Formulated.
Further, described H2O2The concentration of aqueous solution is 20～60%.
Preferably, described H2O2The concentration of aqueous solution is 25～40%.
Most preferably, described H2O2The concentration of aqueous solution is 30%.
Further, the circulation regeneration method of described Ti-HSZ catalyst, including walking as follows
Rapid:
1) Ti-HSZ catalyst is reclaimed
Ti-HSZ catalyst after epoxidation reaction of olefines is reclaimed, through filtration, dried
After, standby；
2) regeneration Ti-HSZ catalyst
By step 1) recycling after Ti-HSZ catalyst and H2O2Aqueous solution and ethanol
Mixed liquor is the ratio mix homogeneously of 1:50～70 in mass ratio, is 25～85 DEG C in temperature
Under conditions of stir 2～36 hours, then through filter, dried, i.e. obtain regeneration Ti-HSZ
Catalyst.
Preferably, described step 2) in, by step 1) Ti-HSZ after recycling
Catalyst and H2O2The mixed liquor of aqueous solution and ethanol is the ratio of 1:55～65 in mass ratio
Mix homogeneously, stirs 6～30 hours under conditions of temperature is 35～70 DEG C, then through filtering,
Dried.
Most preferably, described step 2) in, by step 1) Ti-HSZ catalysis after recycling
Agent and H2O2The mixed liquor of aqueous solution and ethanol is the ratio mixing of 1:60～62 in mass ratio
Uniformly, stir 10～26 hours under conditions of temperature is 45～65 DEG C, then through filtering, doing
Dry process.
Compared with prior art, present invention have the advantage that
The present invention is by using the H of certain proportioning2O2The mixed liquor of aqueous solution and ethanol is to recovery
After Ti-HSZ catalyst treatment, then through filter, be dried catalyst can be made to regenerate, not only
Processing without high-temperature calcination, security performance is high, the recovery time is short, and catalytic regeneration is effective,
Stability is high, can be recycled for multiple times.Additionally, the chloropropene conversion ratio of the Ti-HSZ of regeneration
Reaching 96%, epoxy selectivity reaches 100%, thus regeneration catalyzing activity is high.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1: the circulation regeneration method of a kind of Ti-HSZ catalyst, comprises the steps:
1) Ti-HSZ catalyst is reclaimed
Ti-HSZ catalyst after epoxidation reaction of olefines is reclaimed, through filtration, dried
After, standby；
2) regeneration Ti-HSZ catalyst
By step 1) to take 1g Yu 60.5g regenerated liquid mixed for Ti-HSZ catalyst after recycling
Closing uniformly, wherein regenerated liquid is the H of 30% by 5.5g concentration2O2Aqueous solution and 55g ethanol are joined
System forms, and stirs 10 hours under conditions of temperature is 25 DEG C, then through filtering, being dried place
Reason, i.e. obtains the Ti-HSZ catalyst of regeneration.
Embodiment 2～15
In embodiment 2～15, according to technical scheme provided by the present invention, raw material is joined
Ratio is adjusted in the range of being given, and the performance of the product obtained is suitable, all meets the present invention
Technological thought.Except for the following differences, remaining all with embodiment 1, is shown in Table 1 to implementation process.
Table 1
Embodiment 16: evaluate the regeneration of embodiment 1～15 gained with chloro propylene epoxidation reaction
The stability of Ti-HSZ catalyst.Catalytic reaction condition is: catalyst 0.25 gram, acetone
4.2 gram, chloropropene 2.365 grams, hydrogen peroxide (mass concentration 26.8%) 3.69 grams.Specifically
Process is, catalyst, solvent and reactant is joined in twoport flask successively.At stirring bar
Under part.Hydrogen peroxide is equally divided into four parts.It was sequentially added in reactor in 30 minutes,
60 DEG C are reacted 8 hours.Afterwards, the catalyst recovery process in repetition embodiment 15 times, system
The stability of the catalyst performance after meter repeatedly catalysis, result is as shown in table 2.
Table 2
From table 2 it can be seen that following according to a kind of Ti-HSZ catalyst provided by the present invention
The Ti-HSZ catalyst of ring renovation process gained regeneration, in the epoxidation reaction of catalysis chlorine propylene
In, all show the catalysis activity of excellence.
The above, the only detailed description of the invention of the present invention, it is noted that any be familiar with basis
The technical staff in field in the technical scope that disclosed herein, the change that can readily occur in or
Replace, all should contain within protection scope of the present invention.
Claims (10)
1. the circulation regeneration method of a Ti-HSZ catalyst, it is characterised in that by alkene ring
After Ti-HSZ catalyst after oxidation reaction reclaims, utilize H2O2Aqueous solution and the mixing of ethanol
Liquid cleaning and regeneration.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 1, it is special
Levying and be, described mixed liquor is by H2O2Aqueous solution and ethanol are 1:1～10 preparation in mass ratio
Form.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 2, it is special
Levying and be, described mixed liquor is by H2O2Aqueous solution and ethanol are 1:2～8 preparation in mass ratio
Form.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 3, it is special
Levying and be, described mixed liquor is by H2O2Aqueous solution and ethanol are 1:4～6 preparation in mass ratio
Form.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 1, it is special
Levy and be, described H2O2The concentration of aqueous solution is 20～60%.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 5, it is special
Levy and be, described H2O2The concentration of aqueous solution is 25～40%.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 6, it is special
Levy and be, described H2O2The concentration of aqueous solution is 30%.
8. according to the circulation of the Ti-HSZ catalyst described in claim 1～7 any one again
Generation method, it is characterised in that comprise the steps:
1) Ti-HSZ catalyst is reclaimed
Ti-HSZ catalyst after epoxidation reaction of olefines is reclaimed, through filtration, dried
After, standby；
2) regeneration Ti-HSZ catalyst
By step 1) recycling after Ti-HSZ catalyst and H2O2Aqueous solution and ethanol
Mixed liquor is the ratio mix homogeneously of 1:50～70 in mass ratio, is 25～85 DEG C in temperature
Under conditions of stir 2～36 hours, then through filter, dried, i.e. obtain regeneration Ti-HSZ
Catalyst.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 8, it is special
Levy and be, described step 2) in, by step 1) Ti-HSZ catalyst after recycling with
H2O2The mixed liquor of aqueous solution and ethanol is the ratio mix homogeneously of 1:55～65 in mass ratio,
Stir 6～30 hours under conditions of temperature is 35～70 DEG C, then through filtration, dried.
The circulation regeneration method of Ti-HSZ catalyst the most according to claim 9, its
Be characterised by, described step 2) in, by step 1) recycling after Ti-HSZ catalyst
With H2O2The mixed liquor of aqueous solution and ethanol is that the ratio mixing of 1:60～62 is equal in mass ratio
Even, stir 10～26 hours under conditions of temperature is 45～65 DEG C, then through filtering, being dried
Process.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610139189.1A CN105749966A (en) | 2016-03-11 | 2016-03-11 | Cyclic regeneration method of Ti-HSZ (Ti-containing hollownest-structured zeolite) catalyst |
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| CN201610139189.1A CN105749966A (en) | 2016-03-11 | 2016-03-11 | Cyclic regeneration method of Ti-HSZ (Ti-containing hollownest-structured zeolite) catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237928A (en) * | 2005-07-27 | 2008-08-06 | Sk能源株式会社 | Method of regeneration of titanium-containing molecular sieve catalyst |
| US20100305369A1 (en) * | 2007-05-08 | 2010-12-02 | Basf Se | Process for the preparation of an olefin oxide |
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
-
2016
- 2016-03-11 CN CN201610139189.1A patent/CN105749966A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237928A (en) * | 2005-07-27 | 2008-08-06 | Sk能源株式会社 | Method of regeneration of titanium-containing molecular sieve catalyst |
| US20100305369A1 (en) * | 2007-05-08 | 2010-12-02 | Basf Se | Process for the preparation of an olefin oxide |
| CN105329909A (en) * | 2015-11-30 | 2016-02-17 | 湖北大学 | Method for synthesizing Ti-MWW molecular sieve hollow sphere with high external specific surface area |
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