CN101954275A - Method for preparing catalyst used for gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate - Google Patents
Method for preparing catalyst used for gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate Download PDFInfo
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- CN101954275A CN101954275A CN 201010294522 CN201010294522A CN101954275A CN 101954275 A CN101954275 A CN 101954275A CN 201010294522 CN201010294522 CN 201010294522 CN 201010294522 A CN201010294522 A CN 201010294522A CN 101954275 A CN101954275 A CN 101954275A
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- dimethyl oxalate
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Abstract
The invention relates to a method for preparing a catalyst for the gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate, which comprises the following steps of: slowly adding a silica gel solution to an organic titanate-dispersant solution to completely hydrolyze, filtering, drying, grinding, tabletting, firing and so on to prepare the catalyst. The invention also relates to the application of the catalyst. The catalyst has high reactivity in a gas phase ester exchange reaction between diphenyl oxalate and phenol, the selectivity of diphenyl oxalate is high, the reaction is smooth and easy to control, and the catalyst has simple preparation method, low cost and long service life.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester, this catalyst is prepared by the hydrolytic precipitation method, and be used for the ester exchange reaction of dimethyl oxalate and phenol under the catalyzed gas condition, afterwards reactant liquor is separated to purify obtaining phenostal.
Background technology
Phenostal can be used for the manufacturing raw material of multiple medicine and pesticide intermediate, also can be used as the manufacturing raw material and the additive of polymer, particularly phenostal can decarbonylation diphenyl carbonate synthesis (DPC), and diphenyl carbonate (DPC) is one of important monomer of polycarbonate synthesis (PC).Phenostal can be prepared by the ester exchange reaction of dimethyl oxalate and phenol, and concise and to the point step is described below:
DMO?+?ph-OH MPO?+?MeOH
MPO?+?ph-OH
?DPO?+?MeOH
2MPO?
?DPO?+?DMO
DMO, ph-OH, MPO, MeOH and DPO are respectively dimethyl oxalate, phenol, methyl phenyl oxalate, methyl alcohol and phenostal in last three formulas.
The technology that with this reactions steps is core is obtaining very great development in nearly decades, particularly continual renovation and perfect in selection of catalysts and application is from inorganic metal compound, as cadmium, lead, iron and zinc compound etc., to organo-metallic compound, as organotin and organic titanium etc.; From the homogeneous reaction catalyst to immobilized heterogeneous catalysis etc.These a series of renewals are improved the efficient of ester exchange reaction are improved, and separating of catalyst and reactant liquor becomes easier, but is confined to still formula liquid phase reactor on reaction condition, have influenced the continuity of reaction, are unfavorable for industrialization.Therefore, invent a kind of gas-phase reaction that is used for, environmentally friendly, and be applicable to that the diphenyl oxalate ester catalyst of actual industrial production is extremely important.
Summary of the invention
At above deficiency, the object of the present invention is to provide a kind of method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester, be slowly to add silica gel solution in organic titanate-dispersant solution with the hydrolysis precipitation method, make its complete hydrolysis, after after filtration, oven dry, make after grinding operations such as compressing tablet and calcination.
Technical scheme of the present invention realizes in the following manner: the method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester by weight percentage, may further comprise the steps:
1), dispose organic titanate-dispersant solution: get the dispersant that organic titanate that concentration is 40-60% and concentration is 60-40% and place there-necked flask for each 1 part, slowly stir,
Described organic titanate is butyl titanate or tetraethyl titanate;
Described dispersant is liquid phase alcohols, liquid phase aromatic hydrocarbons or liquid phase ketone;
2), drip silica gel solution: the organic titanate-dispersant solution of step 1) is slowly splashed into concentration when slowly stirring be 20-25% silica gel solution 1.5-3 part, and making content of titanium dioxide is 5%～30%;
3), filter: after being added dropwise to complete, continuing to stir and filter the formation filter cake after 30～60 minutes;
4), grind compressing tablet: with filter cake 60～80 ℃ dry 2～3 hours down, grind a little then, make into uniform powder, the back adds 0.5～1% graphite and carries out compressing tablet, is pressed into granular catalyst;
5), calcination: with granular catalyst 400～500 ℃ of following calcinations 2～3 hours, after be cooled to room temperature, obtain final catalyst.
Described specific surface area of catalyst is 100～300m
2/ g, pore volume are 0.1～0.5cm
3/ g, average pore radius is 5～15nm.
A kind of Application of Catalyst is with the above-mentioned catalyst fixed bed of packing into, carries out the ester exchange reaction synthesis of oxalic acid diphenyl ester of catalysis dimethyl oxalate and phenol under gas phase condition, obtains the high phenostal of purity through separating after purifying.
Catalyst of the present invention has very high reactivity in dimethyl oxalate and phenol gas phase ester exchange reaction, the selectivity of phenostal is very high, reactivity worth is steady, be easy to control, and the Preparation of catalysts method is simple, cost is lower, the catalyst long service life.
The specific embodiment
Embodiment 1:
A kind of method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester, the preparation method concrete steps are as follows: (1) places there-necked flask with butyl titanate-ethanolic solution 500g, butyl titanate concentration is the 50%(percentage by weight), slowly stir; (2) when slowly stirring, slowly splash into the 25%(percentage by weight) silica gel solution 1243g; (3) be added dropwise to complete after, filter after continue stirring 30min; (4) with filter cake dry 2h under 60 ℃, grind a little then, make into uniform powder, the graphite of back adding 0.5% carries out compressing tablet, is pressed into diameter 4mm, the cylindrical particle of height 5mm; (5) granular catalyst that will press sheet is at 400 ℃ of following calcination 3h, after be cooled to room temperature, obtain final catalyst A.The A specific surface area of catalyst is 143m
2/ g, pore volume are 0.2cm
3/ g, average pore radius is 7nm.
Embodiment 2:
A kind of method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester, the preparation method concrete steps are as follows: (1) places there-necked flask with butyl titanate-toluene solution 500g, butyl titanate concentration is the 40%(percentage by weight), slowly stir; (2) when slowly stirring, slowly splash into the 20%(percentage by weight) silica gel solution 1843g; (3) be added dropwise to complete after, filter after continue stirring 45min; (4) with filter cake dry 2.5h under 70 ℃, grind a little then, make into uniform powder, the graphite of back adding 1% carries out compressing tablet, is pressed into diameter 4mm, the cylindrical particle of height 5mm; (5) granular catalyst that will press sheet is at 450 ℃ of following calcination 3h, after be cooled to room temperature, obtain final catalyst B.The B specific surface area of catalyst is 182m
2/ g, pore volume are 0.3cm
3/ g, average pore radius is 9nm.
Embodiment 3:
A kind of method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester, the preparation method concrete steps are as follows: (1) places there-necked flask with butyl titanate-acetone soln 500g, butyl titanate concentration is the 60%(percentage by weight), slowly stir; (2) when slowly stirring, slowly splash into the 25%(percentage by weight) silica gel solution 786g; (3) be added dropwise to complete after, filter after continue stirring 60min; (4) with filter cake dry 3h under 80 ℃, grind a little then, make into uniform powder, the graphite of back adding 1% carries out compressing tablet, is pressed into diameter 4mm, the cylindrical particle of height 5mm; (5) granular catalyst that will press sheet is at 500 ℃ of following calcination 3h, after be cooled to room temperature, obtain final catalyst C.The C specific surface area of catalyst is 217m
2/ g, pore volume are 0.5cm
3/ g, average pore radius is 12nm.
The catalyst performance test
Table 1: gas phase catalytic reaction result
| Catalyst | DMO conversion ratio % | DPO selectivity % |
| A | 56.8 | 84.7 |
| B | 69.2 | 77.5 |
| C | 75.7 | 69.2 |
Through after separating purification, the purity of DPO can reach more than 99% with above-mentioned three kinds of reactant liquors.
Claims (5)
1. the method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester by weight percentage, is characterized in that: may further comprise the steps:
1), disposes organic titanate-dispersant solution: get the dispersant that organic titanate that concentration is 40-60% and concentration is 60-40% and place there-necked flask for each 1 part, slowly stir;
2), drip silica gel solution: the organic titanate-dispersant solution of step 1) is slowly splashed into concentration when slowly stirring be 20-25% silica gel solution 1.5-3 part, and making content of titanium dioxide is 5%～30%;
3), filter: after being added dropwise to complete, continuing to stir and filter the formation filter cake after 30～60 minutes;
4), grind compressing tablet: with filter cake 60～80 ℃ dry 2～3 hours down, grind a little then, make into uniform powder, the back adds 0.5～1% graphite and carries out compressing tablet, is pressed into granular catalyst;
5), calcination: with granular catalyst 400～500 ℃ of following calcinations 2～3 hours, after be cooled to room temperature, obtain final catalyst.
2. the method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester according to claim 1 is characterized in that: the organic titanate in the described step 1) is butyl titanate or tetraethyl titanate.
3. the method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester according to claim 1 is characterized in that: the dispersant described step 2) is liquid phase alcohols, liquid phase aromatic hydrocarbons or liquid phase ketone.
4. the method for preparing catalyst of dimethyl oxalate gas phase catalysis synthesis of oxalic acid diphenyl ester according to claim 1 is characterized in that: the specific surface area of catalyst in the described step 5) is 100～300m
2/ g, pore volume are 0.1～0.5cm
3/ g, average pore radius is 5～15nm.
5. Application of Catalyst according to claim 1 preparation, be with the above-mentioned catalyst fixed bed of packing into, under gas phase condition, carry out the ester exchange reaction synthesis of oxalic acid diphenyl ester of catalysis dimethyl oxalate and phenol, after separating purification, obtain the high phenostal of purity.
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| CN 201010294522 CN101954275A (en) | 2010-09-28 | 2010-09-28 | Method for preparing catalyst used for gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate |
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| CN 201010294522 CN101954275A (en) | 2010-09-28 | 2010-09-28 | Method for preparing catalyst used for gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745212A (en) * | 2017-01-09 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013633B1 (en) * | 1996-03-12 | 2003-05-28 | Ube Industries, Ltd. | Process for producing a diaryl carbonate |
| CN1583246A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate |
| CN1986517A (en) * | 2006-10-23 | 2007-06-27 | 天津大学 | Methyl phenyl oxalate and diphenyl oxalate synthesizing process catalyzed with composite carrier supported metal oxide |
-
2010
- 2010-09-28 CN CN 201010294522 patent/CN101954275A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013633B1 (en) * | 1996-03-12 | 2003-05-28 | Ube Industries, Ltd. | Process for producing a diaryl carbonate |
| CN1583246A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate |
| CN1986517A (en) * | 2006-10-23 | 2007-06-27 | 天津大学 | Methyl phenyl oxalate and diphenyl oxalate synthesizing process catalyzed with composite carrier supported metal oxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745212A (en) * | 2017-01-09 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts |
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Application publication date: 20110126 |