CN101439300A - Regeneration method for deactivated titanium silicon molecular sieve - Google Patents
Regeneration method for deactivated titanium silicon molecular sieve Download PDFInfo
- Publication number
- CN101439300A CN101439300A CNA200710177898XA CN200710177898A CN101439300A CN 101439300 A CN101439300 A CN 101439300A CN A200710177898X A CNA200710177898X A CN A200710177898XA CN 200710177898 A CN200710177898 A CN 200710177898A CN 101439300 A CN101439300 A CN 101439300A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- hts
- regeneration
- molecular sieve
- washing
- 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
Landscapes
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method for regenerating a deactivated titanium-silicon molecular sieve which is characterized by including the steps of separating the deactivated titanium-silicon molecular sieve from an oxidation reaction mixture and washing the deactivated titanium-silicon molecular sieve by water solution of hydrogen peroxide under the temperature between 100 and 200 DEG C and the pressure between 1.0 and 6.0 MPa. The method can shorten the regeneration time and meanwhile the performance of a reclaiming agent can be remarkably increased and improved.
Description
Technical field
The invention relates to a kind of renovation process of deactivated titanium silicon molecular sieve, more specifically say so about the renovation process of deactivated titanium silicon molecular sieve in the kinds of oxidation reaction.
Background technology
Nineteen eighty-three, the TS-1 zeolite molecular sieve of discoveries such as Italian Taramasso is that the selective oxidation of low-carbon alkene opens up a new way.
Domestic and international many researchers have carried out modification to the TS-1 molecular sieve and in the research of aspects such as ammoxidation of cyclohexanone and alkene epoxidation.With the hydrogen peroxide is oxidant, titanium molecular sieve catalysis propylene ring oxidation reaction synthesizing epoxypropane (PO) can have higher conversion ratio and selectivity, this process has the reaction condition gentleness, reaction speed is fast, atom utilization (76%) is higher, and accessory substance is a water, advantages such as environmentally safe, meet the requirement of contemporary Green Chemistry and atom economy idea of development, and be considered to produce the friendly process of PO.But, limited its industrialized application because still there are shortcomings such as the easy inactivation of catalyst in this technology.
EP 0100119 discloses a kind of molecular sieve containing titanium epoxidation of propylene that adopts to prepare the method for expoxy propane.In course of reaction, HTS is easy to inactivation, and this method has proposed two kinds of regenerations, and a kind of is to adopt 550 ℃ of high-temperature roastings, and another kind is to adopt the solvent that uses in methyl alcohol or the course of reaction to wash.Two kinds of renovation process respectively have deficiency, and for example first kind of regeneration at first needs then to cool off after the high-temperature roasting through super-dry at the high-temperature roasting procatalyst, needs to consume big energy and takies equipment; Second kind of regeneration solvent wash needs the time long, and effect is unsatisfactory.
USP5620935 discloses a kind of method that adopts aqueous hydrogen peroxide solution to carry out regenerated from washing, regeneration condition is 40～120 ℃ of hydrogenperoxide steam generator concentration 1～45wt%, wash temperatures, when preferred wash temperature is more than 100 ℃, can reach regeneration effect preferably.But there is the problem that hydrogen peroxide very easily decomposes under the high temperature, utilization ratio reduces greatly in the method, and this method also need consume big energy simultaneously.
The method of the disclosed employing methyl alcohol of USP6878836 B2 high-temperature wash regeneration adopts the wash temperature more than 100 ℃ that deactivator is carried out methanol wash, and regenerative agent can use for a long time, and the selectivity of regenerative agent improves greatly.Keep reaction pressure constant by improving reaction temperature, can obtain the constant hydrogen peroxide conversion and the selectivity of product.The problem that adopts this method to exist mainly is that energy consumption is higher, and regeneration effect is unsatisfactory simultaneously.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the renovation process of deactivated titanium silicon molecular sieve in a kind of oxidation reaction of efficient energy-saving is provided.
Therefore, the method of regeneration of deactivated HTS provided by the invention, it is characterized in that comprising that the HTS with inactivation separates from oxidation mixtures, with 100～200 ℃ of temperature of aqueous hydrogen peroxide solution and the 1.0～6.0MPa pressure step of washing down.
In the method provided by the invention, the HTS of said inactivation is preferably from the epoxidation reaction system, and for example the HTS of inactivation in the propylene ring oxidation reaction can be the HTS of former powder HTS or binding agent moulding.Said epoxidation reaction can be carried out under the combining form of slurry bed, tubular type circulation flow reactor, foaming tower, continuous-flow bed bioreactor or above several reactors.
In the method provided by the invention, behind the HTS inactivation, after filtration, after centrifugal, decant or other suitable methods handle, then make solvent with solvent preferred water or methyl alcohol, more preferably methyl alcohol is that solvent washs in the autoreaction mixed solution; Wash under 100～200 ℃, the pressure of preferred 150～200 ℃ and 1.0～6.0MPa, preferred 3.0～6.0MPa with aqueous hydrogen peroxide solution then, concentration of hydrogen peroxide is 0.01～70wt%, preferred 1～45wt%, more preferably 10～45wt%.
HTS after regeneration can continue to turn back in the oxidation reaction.Regenerative agent is partially or completely separated from aqueous hydrogen peroxide solution, in order to utilize the aqueous hydrogen peroxide solution of regeneration more fully, regeneration back HTS can not separate, in the aqueous hydrogen peroxide solution Returning reactor behind the regenerated from washing, hydrogen peroxide after the regeneration can be further used for oxidation reaction like this, and it is in the propylene ring oxidation reaction of oxidant that this method is particularly useful for the hydrogen peroxide.Method provided by the invention, be equally applicable to adopt the situation of HTS in fixed bed reactors of binding agent moulding, under this condition, the moulding HTS goes regeneration after activity is lost wholly or in part: through solvent wash, 100～200 ℃ of pressurization washings of aqueous hydrogen peroxide solution, aqueous hydrogen peroxide solution can adopt circulation cleaning to recycle, and regenerative agent turns back in the epoxidation reaction.Better mode is before dropping into reaction, adopts solvent to wash once more.The washing solvent for use can be identical or different with solvent for use in the concrete epoxidation reaction.For example the described propylene ring oxidation reaction employing of EP100119 methyl alcohol is solvent, can be that solvent washs with methyl alcohol therefore, also can be water washing.If cleaning solvent is consistent with the epoxidation reaction solvent for use, can separate in advance so, regenerative agent can be turned back in the epoxidation reaction with aqueous hydrogen peroxide solution.If only need partial regeneration, also can adopt according to the present invention and the deactivated titanium silicon molecular sieve in the reactant mixture to be told a part carry out hydrogen peroxide pressurization regenerated from washing, regeneration back regenerative agent returns in the epoxidation reaction.
In the method provided by the invention, regeneration effect that the amount of the hydrogen peroxide that adds reaches according to expection and regenerator design can bear pressure and consider, improve regeneration pressure as far as possible and be beneficial to improve regeneration effect, the regeneration pressure scope of selection is 1.0～6.0MPa, preferred 3.0～6.0MPa.The pressure that is produced comes from closed system from boosting power, also can feed gas medium and further improve system pressure.Said gas medium can be selected from hydrogen, oxygen, nitrogen, helium, argon gas and other any gas, as long as the gas that is added can not react just passable with hydrogen peroxide.
In the method provided by the invention, said pressurization washing process carries out between 100～200 ℃, and regeneration gets final product under the temperature of actual oxidation reaction certainly, at this moment need not heating and cooling operate preferred 150～200 ℃.Recovery time decides with the regeneration temperature that adopts and concentration of hydrogen peroxide and the regeneration effect that seeks out.
Method provided by the invention adopts aqueous hydrogen peroxide solution high temperature pressurization regenerated from washing down, compares with the constant-pressure and high-temperature regenerated from washing, and the recovery time shortens, but regeneration effect is approaching substantially; The more important thing is, the washing of employing high-temperature pressurizing, avoided the invalid decomposition of hydrogen peroxide, still have part hydrogen peroxide residue behind the regeneration ending, can continue to use, make full use of hydrogen peroxide, regeneration back cleaning solution can react with regenerative agent Returning reactor together, save material, reduce cost.
The specific embodiment
Below the present invention is further described but content not thereby limiting the invention by Comparative Examples and embodiment.
Comparative Examples 1
This Comparative Examples explanation catalyst performance evaluation method and decaying catalyst catalytic performance.
Catalyst propylene ring oxidation reaction method of evaluating performance (down together): take by weighing the 0.1g catalyst, 22.8g methanol solution (analyzing pure), 0.5g methyl tertiary butyl ether(MTBE) (internal standard compound), 2.5g hydrogen peroxide (30wt%) adds in the autoclave of belt stirrer.Employing water-bath heating, setting bath temperature is 40 ℃.Open stirring, turn up 800r.min
～1After, logical propylene keep-ups pressure and is 0.3MPa in reactor.Behind the reaction 0.5h, cool off fast below temperature of reaction kettle to 15～16 ℃, remove and press off still with frozen water.
Adopt hydrogen peroxide conversion as the catalyst performance evaluation index.Hydrogen peroxide mass fraction with feed liquid before and after the iodometry mensuration calculates hydrogen peroxide conversion.
It is 17.6% that the sample that decaying catalyst provides for the industrial experiment device, evaluation experimental record hydrogen peroxide conversion.
Comparative Examples 2
This Comparative Examples explanation fresh titanium silicon molecular sieve catalytic active.
It is 55.01% that evaluation experimental records hydrogen peroxide conversion.
Comparative Examples 3
This Comparative Examples explanation prior art high-temperature roasting regeneration titanium molecular sieve catalysis activity.
The condition of decaying catalyst high-temperature roasting regeneration is 550 ℃, 3h, and it is 47.41% that evaluation experimental records hydrogen peroxide conversion.
Comparative Examples 4
The catalytic activity of this Comparative Examples explanation prior art normal pressure methanol wash regeneration HTS.
The 5g decaying catalyst adopts 100 ℃ of normal pressure washings of 50g methyl alcohol 4h, then filters.
It is 23.94% that evaluation experimental records hydrogen peroxide conversion.
Comparative Examples 5
The catalytic activity of this Comparative Examples explanation prior art normal pressure hydrogen peroxide regenerated from washing HTS.
The 5g decaying catalyst adopts 100 ℃ of normal pressure washings of 100g hydrogen peroxide (5wt%) 7h, then filters, and the residual concentration of hydrogen peroxide is 0.1%.
It is 45.53% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 1
The 5g decaying catalyst adopts 100 ℃ of closed systems of 100g hydrogen peroxide (30wt%), and pre-inflated with nitrogen is kept system pressure 3.0～4.0Mpa, and pressurization washing 4h then filters, and the residual concentration of hydrogen peroxide is 2.1%.
It is 41.02% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 2
The decaying catalyst of 5g example 3 adopts 150 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 3.0～4.0Mpa, and pressurization washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.8%.
It is 43.02% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 3
The 5g decaying catalyst adopts 200 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 3.0～4.0Mpa, and pressurization washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.6%.
It is 46.26% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 4
The 5g decaying catalyst adopts 100 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 4.0～5.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 2.0%.
It is 42.50% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 5
The 5g decaying catalyst adopts 150 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 4.0～5.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.75%.
It is 45.00% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 6
The 5g decaying catalyst adopts 150 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 4.0～5.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.4%.
It is 47.50% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 7
The 5g decaying catalyst adopts 200 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 5.0～6.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.9%.
It is 45.00% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 8
The 5g decaying catalyst adopts 200 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 5.0～6.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.6%.
It is 47.50% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Embodiment 9
The 5g decaying catalyst adopts 200 ℃ of closed systems of 100g hydrogen peroxide (5%wt), and pre-inflated with nitrogen is kept system pressure 5.0～6.0Mpa, and washing 4h then filters, and the residual concentration of hydrogen peroxide is 1.3%.
It is 48.70% that the epoxidation evaluation experimental records hydrogen peroxide conversion.
Claims (9)
1, a kind of method of regeneration of deactivated HTS is characterized in that comprising that the HTS with inactivation separates from oxidation mixtures, with 100～200 ℃ of temperature of aqueous hydrogen peroxide solution and the 1.0～6.0MPa pressure step of washing down.
2, according to the process of claim 1 wherein that said HTS is the HTS of former powder HTS or binding agent moulding.
3,, it is characterized in that aqueous hydrogen peroxide solution concentration is 0.01～70wt% according to the method for claim 1.
4,, it is characterized in that aqueous hydrogen peroxide solution concentration is 1～45wt% according to the method for claim 3.
5,, it is characterized in that the temperature that regenerated from washing adopts is 150～200 ℃ according to the method for claim 1.
6,, it is characterized in that pressure is 3.0～6.0MPa according to the method for claim 1.
7,, it is characterized in that feeding gas medium and further improve system pressure, the gas of said gas medium for not reacting with hydrogen peroxide according to the method for claim 1 or 6.
8, according to the method for claim 7, said gas is selected from hydrogen, oxygen, nitrogen, helium or argon gas.
9, according to the method for claim 1, said oxidation reaction is a propylene ring oxidation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710177898XA CN101439300A (en) | 2007-11-22 | 2007-11-22 | Regeneration method for deactivated titanium silicon molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710177898XA CN101439300A (en) | 2007-11-22 | 2007-11-22 | Regeneration method for deactivated titanium silicon molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101439300A true CN101439300A (en) | 2009-05-27 |
Family
ID=40723988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200710177898XA Pending CN101439300A (en) | 2007-11-22 | 2007-11-22 | Regeneration method for deactivated titanium silicon molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101439300A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941117A (en) * | 2012-11-13 | 2013-02-27 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve catalyst |
| CN104415743A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Regenerating method of titanium-containing catalyst |
| CN105413745A (en) * | 2015-12-28 | 2016-03-23 | 郑州大学 | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst |
| CN104876797B (en) * | 2014-02-28 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of propylene glycol |
-
2007
- 2007-11-22 CN CNA200710177898XA patent/CN101439300A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941117A (en) * | 2012-11-13 | 2013-02-27 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve catalyst |
| CN104415743A (en) * | 2013-09-09 | 2015-03-18 | 中国石油化工股份有限公司 | Regenerating method of titanium-containing catalyst |
| CN104415743B (en) * | 2013-09-09 | 2017-02-01 | 中国石油化工股份有限公司 | Regenerating method of titanium-containing catalyst |
| CN104876797B (en) * | 2014-02-28 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of propylene glycol |
| CN105413745A (en) * | 2015-12-28 | 2016-03-23 | 郑州大学 | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101455980B (en) | Regeneration method of oxidation-reaction inactive titanium silicon molecule sieve catalyst | |
| CN105418561B (en) | A kind of method that support type bifunctional catalyst catalysis fructose prepares 2,5 furandicarboxylic acids | |
| CN1196660C (en) | Process for preparing cumene which is used in the preparation of phenol | |
| CN101274922A (en) | Preparation for epoxypropane | |
| CN107721913A (en) | A kind of preparation method of 2,3 dichloropyridine | |
| CN101439300A (en) | Regeneration method for deactivated titanium silicon molecular sieve | |
| CN103182322B (en) | A kind of method processing deactivated titanium silicon molecular sieve | |
| CN103193589A (en) | Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis | |
| CN101992125B (en) | Method for regenerating heteropoly acid quaternary ammonium salt catalyst | |
| CN103373979B (en) | Catalytic reaction method for producing lactones | |
| CN101439301B (en) | Method for regenerating catalyst by low-temperature oxidation using perchloric acid | |
| CN102951998A (en) | Method of preparing glycol by using one-step ethylene method | |
| CN100553779C (en) | A kind of unsaturated aldehyde hydrogen transfer reduction prepares the recovery method of pure Al catalysts in the unsaturated alcohol reaction | |
| CN101314137A (en) | Regeneration method for deactivated titanium silicon molecular sieve | |
| CN102381922B (en) | Method for compounding ethylene by ethanol | |
| CN101439299B (en) | Catalyst regeneration process | |
| CN103664557A (en) | Method for preparing cyclopentanone by oxidation of cyclopentene | |
| CN103373915B (en) | A kind of catalytic oxidation prepares the method for di-carboxylic acid | |
| CN102381927B (en) | Method for synthesizing phenylethane from ethanol | |
| CN102093180B (en) | Method for continuously producing unsaturated aldehyde compound | |
| CN101455981B (en) | Improved titanium-containing catalyst regeneration method | |
| CN110183300A (en) | A kind of process and system by the highly selective propylene processed of synthesis gas | |
| JP3866005B2 (en) | Biogas treatment method | |
| AU6702400A (en) | Process for preparing alkylene oxide | |
| CN102190563A (en) | Method for preparing alpha-phenethyl alcohol by using supported zirconium oxide as catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090527 |