CN101439301B - Method for regenerating catalyst by low-temperature oxidation using perchloric acid - Google Patents
Method for regenerating catalyst by low-temperature oxidation using perchloric acid Download PDFInfo
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- CN101439301B CN101439301B CN2007101778994A CN200710177899A CN101439301B CN 101439301 B CN101439301 B CN 101439301B CN 2007101778994 A CN2007101778994 A CN 2007101778994A CN 200710177899 A CN200710177899 A CN 200710177899A CN 101439301 B CN101439301 B CN 101439301B
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Abstract
The invention discloses a method for regenerating a catalyst by the lower temperature oxidization of perchloric acid which is characterized in that after a deactivated titanium-silicon molecular sieve catalyst is washed by an organic solvent, the catalyst is filtered, dried and then is arranged into a high temperature resistance container; then perchloric acid solution with the concentration of 0.01 to 1mol/l with a weight ratio of 1 to 3: 1 to the catalyst is added to contact air or oxygen under the temperature between 100 and 300 DEG C for 2 to 8h.
Description
Technical field
The present invention relates to a kind of renovation process of decaying catalyst, more particularly, the invention relates to a kind of renovation process that is used for the inactive titanium silicon molecule sieve catalyst of oxidation reaction.
Background technology
Nineteen eighty-three Italy scientist Taramasso etc. has found to have the HTS of MFI structure, and it shows excellent catalytic performance in catalytic oxidation.After this, HTS is widely used in the reaction of adopting hydrogen peroxide and organic matter direct oxidation, as the Ammoximation reaction of aromatic hydrocarbons, alkene, alcohols, nitrogen-containing compound and carbonyl containing compound etc.Yet in operation a period of time rear catalyst catalytic performance meeting variation, deactivation phenomenom appears in catalyst usually.The reason that causes catalysqt deactivation may be because impurity of introducing in the synthesis of molecular sieve process or byproduct of reaction accumulate in the interior plug-hole of catalyst micropore etc.
EP 0100119 discloses a kind of molecular sieve containing titanium epoxidation of propylene that adopts to prepare the method for expoxy propane.M.G.Clerici etc. point out that in course of reaction, HTS is easy to inactivation, and two kinds of renovation process are arranged, and a kind of is the method that adopts 550 ℃ of high-temperature roastings, and another kind is the method that adopts the solvent wash that uses in methyl alcohol or the course of reaction.Two kinds of renovation process respectively have weak point, and first kind of renovation process 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 renovation process 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, adopt the regeneration condition of 40～120 ℃ of hydrogenperoxide steam generator concentration 1～45wt%, wash temperature, when preferably regeneration temperature is more than 100 ℃, can reach regeneration effect preferably, have quick, characteristic of simple.But the subject matter that the method exists is that hydrogen peroxide very easily decomposes under the high temperature, causes the hydrogen peroxide utilization ratio to reduce greatly.Simultaneously, this method need consume big energy equally.
The method of the disclosed employing methyl alcohol of USP6878836B2 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.
CN1461671A discloses a kind of renovation process of titanium-containing catalyst, be in the acid flux material of pH≤3, to handle decaying catalyst, said acid solution be inorganic acid with the mixed liquor of hydrogen peroxide, the concentration 0～10wt% of hydrogen peroxide in the mixed liquor.
Summary of the invention
The objective of the invention is provides a kind of renovation process of efficient energy-saving on the basis of prior art solvent wash.
The method of regenerated catalyst provided by the invention, after it is characterized in that titanium-silicon molecular sieve catalyst with inactivation is with organic solvent washing, drying after filtration,, again catalyst is placed high-temperature resistant container, add concentration then and be 0.01～1mol/l, with the mass ratio of catalyst be 1～3: 1 perchloric acid solution, contact 2～8h with air or oxygen down for 100～300 ℃ in temperature.
In the method provided by the invention, the titanium-silicon molecular sieve catalyst of inactivation being separated from reactant mixture, is that solvent washs with organic solvent, particular methanol at first.Wash temperature is usually selected to equal or the boiling point of a little higher than organic solvent, and washing process is preferably in airtight self-generated pressure washing down in the container.Wash time was generally 30 minutes to 2 hours.After adopting organic solvent washing to finish, preferably then wash with water, wash time is no more than 30 minutes.
The titanium-silicon molecular sieve catalyst of inactivation is behind organic solvent washing, filtration, drying, place high-temperature resistant container, the quality proportioning of interpolation and catalyst is 1～3 perchloric acid solution then, and the concentration of perchloric acid is 0.01～1.0mol/l, preferred 0.1～1.0mol/l, move in the heating furnace, temperature is 100～300 ℃, preferred 200～300 ℃ of bubbling airs or oxygen atmosphere, can be pure oxygen atmosphere, also can or be connected with in the atmosphere of minor amounts of oxygen at air and carry out.Regenerative operation should suitably be controlled programming rate, should not be too fast, and this can guarantee perchloric acid solution and catalyst even contact, the also danger that can have been avoided perchloric acid at high temperature to blast.Simultaneously, in the regenerative process, should guarantee that the high-temperature resistant container that catalyst and perchloric acid solution are housed leaves certain gas-phase space, prevent that catalyst acutely makes quick-fried the spattering of catalyst cause damage with contacting of perchloric acid in the regenerative process.Processing time becomes with the catalysqt deactivation state, is generally 2～8h, preferred 3～6h.
The inactive titanium silicon molecule sieve catalyst that the present invention handles can be from the oxidation reaction that adopts hydrogen peroxide and organic reactant, the titanium-silicon molecular sieve catalyst of inactivation in preferred alkenes epoxidation, aromatic hydrocarbons hydroxylating, the cyclohexanone oxamidinating reaction.
Method provided by the invention is to carry out oxidation regeneration with this strong oxidizer of perchloric acid, only needs perchloric acid and catalyst are soaked, and low-temperature bake gets final product, and need not to resemble the washing of hydrogen peroxide equal solvent needs intensively stirred mode, operates simple relatively.Adopt renovation process provided by the invention, under the 100 ℃ of conditions that coexist, perchloric acid oxidation's regeneration effect is better than organic solvent washing regeneration effect (Comparative Examples 4); And under 200～300 ℃ of conditions, through oxidation regeneration, its regeneration effect and high-temperature roasting regeneration effect have reached the purpose that reduces energy loss near (Comparative Examples 3).
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
The method of evaluating performance and the decaying catalyst catalytic activity of the catalyst of this Comparative Examples explanation propylene ring oxidation reaction.
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.Liquid product chromatograph after centrifugal is formed, adopt iodometry measure before and after the hydrogen peroxide mass fraction of feed liquid, calculate hydrogen peroxide conversion.
Adopt hydrogen peroxide conversion as the catalyst activity evaluation index.
It is 17.60% that the sample that decaying catalyst provides for the industrial experiment device, evaluation experimental record hydrogen peroxide conversion.
Comparative Examples 2
The catalytic activity of this Comparative Examples explanation fresh titanium silicalite molecular sieve catalyst.
Epoxidation reaction evaluation such as Comparative Examples 1 are narrated.It is 55.01% that evaluation experimental records fresh titanium silicalite molecular sieve catalyst hydrogen peroxide conversion.
Comparative Examples 3
The catalytic activity of this Comparative Examples explanation high-temperature roasting regeneration titanium-silicon molecular sieve catalyst.
Epoxidation reaction evaluation such as Comparative Examples 1 are narrated, and the condition of decaying catalyst high-temperature roasting regeneration is 550 ℃ of 3h.It is 47.41% that evaluation experimental records regeneration back hydrogen peroxide conversion.
Comparative Examples 4
The catalytic activity of this Comparative Examples explanation normal pressure methanol wash regeneration titanium-silicon molecular sieve catalyst.
The 5g decaying catalyst adopts 100 ℃ of normal pressure washings of 50g methyl alcohol 4h.
Epoxidation reaction evaluation such as Comparative Examples 1 are narrated, and it is 23.94% that evaluation experimental records hydrogen peroxide conversion.
Comparative Examples 5
The catalytic activity of this Comparative Examples explanation normal pressure hydrogen peroxide regenerated from washing titanium-silicon molecular sieve catalyst.
The 5g decaying catalyst adopts 100 ℃ of normal pressure washings of 100g hydrogen peroxide (30wt%) 7h.
Epoxidation reaction evaluation such as Comparative Examples 1 are narrated, and it is 45.53% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 1
The 5g decaying catalyst places crucible, behind the interpolation 5g perchloric acid solution (0.01mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 100 ℃ permanent 2h.It is 25.00% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 2
The 5g decaying catalyst places crucible, behind the interpolation 10g perchloric acid solution (0.1mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 100 ℃ permanent 3h.It is 30.00% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 3
The 5g decaying catalyst places crucible, behind the interpolation 15g perchloric acid solution (1.0mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 100 ℃ permanent 8h.It is 35.50% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 4
The 5g decaying catalyst places crucible, behind the interpolation 5g perchloric acid solution (0.01mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 200 ℃ permanent 3h.It is 35.70% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 5
The decaying catalyst of 5g places crucible, behind the interpolation 10g perchloric acid solution (0.1mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 200 ℃ permanent 6h.It is 40.50% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 6
The decaying catalyst of 5g places crucible, behind the interpolation 15g perchloric acid solution (1.0mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 200 ℃ permanent 8h.It is 42.80% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 7
The decaying catalyst of 5g places crucible, behind the interpolation 5g perchloric acid solution (0.01mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 300 ℃ permanent 2h.It is 42.70% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 8
The decaying catalyst of 5g places crucible, behind the interpolation 10g perchloric acid solution (0.1mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 300 ℃ permanent 6h.It is 45.80% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 9
The decaying catalyst of 5g places crucible, behind the interpolation 15g perchloric acid solution (1.0mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 300 ℃ permanent 8h.It is 48.50% that evaluation experimental records hydrogen peroxide conversion.
Embodiment 10
The decaying catalyst of 5g places crucible, behind the interpolation 15g perchloric acid solution (1.0mol/l), adds an iron plate and places the crucible top, guarantees that part covers crucible, moves to crucible in the Muffle furnace 3h temperature programming to 300 ℃ permanent 6h.It is 48.70% that evaluation experimental records hydrogen peroxide conversion.
Claims (2)
1. the method for a regenerated catalyst, after it is characterized in that titanium-silicon molecular sieve catalyst with inactivation is with organic solvent washing, drying after filtration,, again catalyst is placed high-temperature resistant container, add concentration then and be 0.01～1mol/l, with the mass ratio of catalyst be 1～3: 1 perchloric acid solution, contact 2～8h with air or oxygen down for 100～300 ℃ in temperature.
2. according to the method for claim 1, the concentration that it is characterized in that perchloric acid is 0.1～1.0mol/l.
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| CN2007101778994A CN101439301B (en) | 2007-11-22 | 2007-11-22 | Method for regenerating catalyst by low-temperature oxidation using perchloric acid |
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| CN2007101778994A CN101439301B (en) | 2007-11-22 | 2007-11-22 | Method for regenerating catalyst by low-temperature oxidation using perchloric acid |
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| CN101439301A CN101439301A (en) | 2009-05-27 |
| CN101439301B true CN101439301B (en) | 2011-07-20 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102309983B (en) * | 2010-06-30 | 2013-07-31 | 中国石油化工股份有限公司 | Method for regenerating inactivated titanium silicon molecular sieve |
| CN102309982B (en) * | 2010-06-30 | 2013-09-04 | 中国石油化工股份有限公司 | Steam regeneration method of deactivated titanium-silicon molecular sieve |
| CN102309981B (en) * | 2010-06-30 | 2013-07-31 | 中国石油化工股份有限公司 | Hydrothermal regenerating method of titanium silicon molecular sieve |
| EP2600971A4 (en) | 2010-08-03 | 2014-12-24 | Aditya Birla Science And Technology Company Ltd | A process for regeneration of silicate catalyst |
| CN106146262B (en) * | 2015-03-24 | 2018-11-30 | 中国石油化工股份有限公司 | A method of preparing propylene glycol monomethyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753576A (en) * | 1995-05-18 | 1998-05-19 | Arco Chemical Technology, L.P. | Regeneration of a titanium-containing molecular sieve |
| US6063941A (en) * | 1996-10-25 | 2000-05-16 | Solvay (Societe Anonyme) | Process for the regeneration of catalysts |
| CN1809547A (en) * | 2003-06-18 | 2006-07-26 | 德古萨股份公司 | Process for the epoxidation of propene |
| CN1921938A (en) * | 2004-02-24 | 2007-02-28 | 利安德化学技术有限公司 | Catalyst regeneration process |
-
2007
- 2007-11-22 CN CN2007101778994A patent/CN101439301B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753576A (en) * | 1995-05-18 | 1998-05-19 | Arco Chemical Technology, L.P. | Regeneration of a titanium-containing molecular sieve |
| US6063941A (en) * | 1996-10-25 | 2000-05-16 | Solvay (Societe Anonyme) | Process for the regeneration of catalysts |
| CN1809547A (en) * | 2003-06-18 | 2006-07-26 | 德古萨股份公司 | Process for the epoxidation of propene |
| CN1921938A (en) * | 2004-02-24 | 2007-02-28 | 利安德化学技术有限公司 | Catalyst regeneration process |
Non-Patent Citations (1)
| Title |
|---|
| Qingfa Wang，et.al.Deactivation and regeneration of titanium silicalite catalyst for epoxidation of propylene.《Journal of Molecular Catalysis A: Chemical》.2007,73-80. * |
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