CN107715900A - Sol method prepares the low vanadium catalyst of multicomponent of pyromellitic acid dianhydride - Google Patents
Sol method prepares the low vanadium catalyst of multicomponent of pyromellitic acid dianhydride Download PDFInfo
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- CN107715900A CN107715900A CN201710918712.5A CN201710918712A CN107715900A CN 107715900 A CN107715900 A CN 107715900A CN 201710918712 A CN201710918712 A CN 201710918712A CN 107715900 A CN107715900 A CN 107715900A
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- catalyst
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- pyromellitic acid
- acid dianhydride
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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Abstract
The present invention discloses the low vanadium catalyst of multicomponent that a kind of sol method prepares pyromellitic acid dianhydride.Major catalyst is V in the catalyst2O5And TiO2, V：Ti mol ratios are 0.05：1~0.15：1；In the catalyst, co-catalyst B2O3、SnO2And CeO2, using the amount benchmark of V material as 1, wherein the amount of B material is that the amount that the amount of 0.001 0.1, Sn material is 0.001 0.1, Ce material is 0.001 0.1, and the catalyst carrier is the 6mm of ￠ 5 SiC.The procedure that the present invention uses is simple, and raw material is extensive, can largely prepare that particle is relatively thin, the catalyst that selectivity is good, content of vanadium is relatively low, suitable for the application in durol gaseous oxidation.
Description
Technical field
The present invention relates to technical field of chemistry, and in particular to a kind of catalyst and preparation method thereof, in particular for preparing
The catalyst of pyromellitic acid dianhydride.
Background technology
At present, the preparation method of equal acid anhydride mainly has three kinds, respectively durol oxidizing process, pseudocumene alkylation process and
Carbon monoxide method.Wherein industrially using it is relatively broad be durol vapour phase oxidation process, its advantage is only to need a step
Equal acid anhydride is made, technique is simple；Using air as oxidant, it can continuously prepare, be easy to industrial production.
The conventional preparation technology for preparing equal acid anhydride catalyst has spraying process, infusion process etc..Typically to the preparation of equal acid anhydride catalyst
Using spraying process, it is standby that each component is mixed and made into by suspension with predetermined ratio, then with spray gun by suspension spray to carrier
Surface forms certain thickness, last calcination activation catalyst.
Catalytic gas phase oxidation durol produces pyromellitic acid anhydride used catalyst at present with V2O5For major catalyst,
And it is co-catalyst to be aided with other metal oxides.Deng state is just waited with V2O5Based on, prepared supplemented by Ti, Nd, P, Cs oxide
The catalyst gone out reaction temperature (460 ± 10) DEG C, 6000~8000h- of air speed, the aerial concentration of durol (20 ±
3)g/m3When, the yield of solids crude acid anhydride is up to 95%~100%, and the quality of product is good, accessory substance is few, is easy to refined purification.Should
Catalyst has the characteristics of favorable reproducibility, stability are high, service life is long.Patent US 5225572 is prepared for a series of V2O5-
TiO2For the composite catalyst of main component, under the conditions of 350~380 DEG C, 4000h-, 0.5% B is added2O3Equal acid anhydride is made
Optimum molar yield be 60.5%, purity 95%.Research is found, as reaction temperature raises, molar yield reduces, but its
Purity increase.
In the preparation method of nanocatalyst hydro-thermal method can by reaction condition selection come control the particle diameter of product and its
Performance.Hydro-thermal method refers in the closed container of HTHP, the chemical reaction carried out using water as medium.And microwave-hydrothermal method
To be combined together traditional hydro-thermal method with microwave, have firing rate it is fast, be quick on the draw, be heated system it is uniform the features such as,
The nano-particle that particle diameter distribution is narrow, form is homogeneous can quickly be prepared.
At present, the catalyst industrially used is with V2O5-TiO2Based on, the composite catalyst supplemented by other oxides, but
Because the catalyst granules produced is larger, poor selectivity, yield can be caused relatively low.In addition, V2O5With certain toxicity, should try one's best
Catalyst activity is improved while reducing the relative amount of vanadium and then improves the yield and purity of equal acid anhydride.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of particle is relatively thin, the catalysis that selectivity is good, content of vanadium is relatively low
Agent and the catalyst is produced into pyromellitic acid anhydride for durol gaseous oxidation.
In order to solve the above technical problems, the technical scheme of first aspect present invention is：A kind of sol method prepares pyromellitic acid
The low vanadium catalyst of multicomponent of dianhydride, including major catalyst and co-catalyst, the major catalyst are V2O5And TiO2, V：Ti rubs
You are than being 1：0.1~1：5；Co-catalyst is B2O3、SnO2And CeO2, using the amount benchmark of V material as 1, then the amount of B material
For 0.001-0.1, the amount of Sn material is 0.001-0.1, and the amount of Ce material is 0.001-0.1.
Preferably, major catalyst and co-catalyst are sprayed on carrier respectively by proportioning, and the carrier is ￠ 5-6mm's
SiC。
Preferably, the TiO2For nano-anatase TiO2。
Preferably, V：Ti mol ratios are 1：0.5~1：3.
The method that pyromellitic acid anhydride is produced in durol gaseous oxidation is：It is anti-that 50ml catalyst is loaded into ￠ 40mm
Ying Guanzhong, 430-450 DEG C of furnace temp is controlled, is passed through the min-20min of air 5 in advance so that a small amount of organic matter in catalyst
Decompose, cellular can be formed on catalyst activity top layer；Durol is passed through, carries out catalysis oxidation with air, air speed exists
4500-4900h-1, product yield of every 2 hours measure, it is 87-95% to obtain product highest weight yield, pyromellitic acid two
Acid anhydride content is 94% or so.
The method for preparing Above-mentioned catalytic agent, it comprises the following steps：
(1) ammonium metavanadate is added into oxalic acid solution, is reduced into former vanadium at a certain temperature；
(2) it is 2-3 to adjust previous solu pH, adds the butyl titanate solution for being dissolved in absolute ethyl alcohol, makes V：Ti mol ratios
For 1：0.1~1：5, V-Ti colloidal sols are made in controlling reaction temperature；
(3) using the amount benchmark of V material as 1, boric acid, five four chlorinations of hydration are added into foregoing V-Ti colloidal sols in molar ratio
Tin and six nitric hydrate ceriums, are made into colloidal sol spray coating liquor；
(4) the colloidal sol spray coating liquor that step (3) obtains is sprayed on carrier, is then placed in calcination activation.
In step (1), former vanadium is reduced at 80-90 DEG C.
In step (2), controlling reaction temperature is 80-90 DEG C.
In step (4), the carrier is previously heated to 230-250 DEG C before spraying；The roasting condition is to be protected at 250 DEG C
Temperature 30 minutes, it is further continued for being warming up to 480 DEG C and is calcined 2 hours.
The invention has the advantages that：
The preparation of catalyst prepares spray coating liquor then calcination activation, the catalyst of preparation using sol method in the present invention
For purity is high, the multicomponent nanocomposite particle that particle diameter distribution is uniform, chemism is big, so as to improve the selectivity of the catalyst and
Yield.Catalytic mechanical intensity prepared by this method is high, and catalyst surface active layer is not easy during transport catalyst, filling
Fragmentation.The catalyst shows in use, is 4500-4900h in space time velocity-1When, the hot(test)-spot temperature of durol is 430-
Under conditions of 450 DEG C, obtained pyromellitic acid anhydride highest weight yield is 87-95%, and pyromellitic acid dianhydride purity exists
95% or so.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, unreceipted implementation condition is usually the condition in normal experiment.
Introduce and summarize
The present invention by way of example rather than provides the mode of limitation to illustrate.It should be noted that in present disclosure
Described " one " or " one kind " embodiment is not necessarily referring to same embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art, can
Implement the present invention according to the only some or all of aspects of the present invention.For purposes of illustration, provide herein specific numbering, material and
Configuration, enables one to thoroughly understand the present invention.However, be evident that for those of skill in the art,
The present invention can be implemented without concrete details.In other examples, not make the present invention is obscure many institutes have been omitted or simplified
Known feature.
Various operations are described successively as multiple discrete steps, and with most helpful in the side for understanding the present invention
Formula illustrates；However, in-order description should not be construed as to imply that these operations are necessarily dependent on order.
Reactant according to type species is illustrated to various embodiments.To show for those of skill in the art and
It is clear to, any number of different types of reactant can be used to implement for the present invention, and be more than those for the purpose of illustration
And the reactant provided herein.In addition, also it is evident that, the invention is not limited in any specific mixing is shown
Example.
Embodiment 1：Ammonium metavanadate is added into oxalic acid solution, former vanadium is reduced at 80-90 DEG C, salt acid for adjusting pH is added dropwise
For 2-3, the butyl titanate solution for being dissolved in absolute ethyl alcohol is added, makes V：Ti mol ratios are 1：0.5, V-Ti is made in controlling reaction temperature
Colloidal sol；1 on the basis of the amount of V material, B (B are added in molar ratio2O3) it is 0.01, Sn (SnO2) it is 0.02, Ce (CeO2) be
0.022, it is sprayed on after being made into colloidal sol spray coating liquor on the SiC for the ￠ 5-6mm for being previously heated to 230-250 DEG C.It is then placed in
30 minutes are incubated at 250 DEG C in Muffle furnace, is further continued for being warming up to 480 DEG C and is calcined 2 hours.Cooling, take out stand-by.
Catalyst is fitted into ￠ 40mm reaction tubes, 430-450 DEG C of furnace temp is controlled, is passed through air 5min in advance,
So that a small amount of organic matter decomposes in catalyst, cellular can be formed on catalyst activity top layer.Durol is passed through, uses air
Catalysis oxidation is carried out, air speed is in 4500-4900h-1, product yield of every 2 hours measure, obtain product highest weight yield
For 88-90%, pyromellitic acid dianhydride content is 94% or so.
Embodiment 2：Ammonium metavanadate is added into oxalic acid solution, former vanadium is reduced at 80-90 DEG C, salt acid for adjusting pH is added dropwise
For 2-3, the butyl titanate solution for being dissolved in absolute ethyl alcohol is added, makes V：Ti mol ratios are 1：1, it is molten that V-Ti is made in controlling reaction temperature
Glue；1 on the basis of the amount of V material, B (B are added in molar ratio2O3) it is 0.015, Sn (SnO2) it is 0.031, Ce (CeO2) be
0.04, it is sprayed on after being made into colloidal sol spray coating liquor on the SiC for the ￠ 5-6mm for being previously heated to 230-250 DEG C.It is then placed in horse
30 minutes not are incubated at 250 DEG C in stove, is further continued for being warming up to 480 DEG C and is calcined 2 hours.Cooling, take out stand-by.
Catalyst is fitted into ￠ 40mm reaction tubes, 430-450 DEG C of furnace temp is controlled, is passed through air 5min in advance,
So that a small amount of organic matter decomposes in catalyst, cellular can be formed on catalyst activity top layer.Durol is passed through, uses air
Catalysis oxidation is carried out, air speed is in 4500-4900h-1, product yield of every 2 hours measure, obtain product highest weight yield
For 92-95%, pyromellitic acid dianhydride content is 95% or so.
Embodiment 3：Ammonium metavanadate is added into oxalic acid solution, former vanadium is reduced at 80-90 DEG C, salt acid for adjusting pH is added dropwise
For 2-3, the butyl titanate solution for being dissolved in absolute ethyl alcohol is added, makes V：Ti mol ratios are 1：3, it is molten that V-Ti is made in controlling reaction temperature
Glue；1 on the basis of the amount of V material, B (B are added in molar ratio2O3) it is 0.02, Sn (SnO2) it is 0.041, Ce (CeO2) be
0.053, it is sprayed on after being made into colloidal sol spray coating liquor on the SiC for the ￠ 5-6mm for being previously heated to 230-250 DEG C.It is then placed in
30 minutes are incubated at 250 DEG C in Muffle furnace, is further continued for being warming up to 480 DEG C and is calcined 2 hours.Cooling, take out stand-by.
Catalyst is fitted into ￠ 40mm reaction tubes, 430-450 DEG C of furnace temp is controlled, is passed through air 5min in advance,
So that a small amount of organic matter decomposes in catalyst, cellular can be formed on catalyst activity top layer.Durol is passed through, uses air
Catalysis oxidation is carried out, air speed is in 4500-4900h-1, product yield of every 2 hours measure, obtain product highest weight yield
For 87-90%, pyromellitic acid dianhydride content is 94% or so.
Specific embodiment described above is only the preferred embodiment of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement or replacement can also be made, these improvement
Or replace and should also be as being considered as protection scope of the present invention.
Claims (5)
1. the low vanadium catalyst of multicomponent of pyromellitic acid dianhydride prepared by a kind of sol method, it is characterised in that including major catalyst
And co-catalyst, the major catalyst are V2O5And TiO2, V：Ti mol ratios are 1：0.1~1：5；Co-catalyst is B2O3、SnO2
And CeO2, using the amount benchmark of V material as 1, then the amount of B material is 0.001-0.1, and the amount of Sn material is 0.001-0.1,
The amount of Ce material is 0.001-0.1.
2. the low vanadium catalyst of multicomponent according to claim 1, it is characterised in that major catalyst and co-catalyst are by proportioning
It is sprayed on respectively on carrier.
3. the low vanadium catalyst of multicomponent according to claim 2, it is characterised in that the carrier is ￠ 5-6mm SiC.
4. the low vanadium catalyst of multicomponent according to claim 1, it is characterised in that the TiO2For nano-anatase
TiO2。
5. the low vanadium catalyst of multicomponent according to claim 1, it is characterised in that V：Ti mol ratios are 1：0.5~1：3.
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| CN201710918712.5A CN107715900A (en) | 2017-09-30 | 2017-09-30 | Sol method prepares the low vanadium catalyst of multicomponent of pyromellitic acid dianhydride |
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| CN201710918712.5A CN107715900A (en) | 2017-09-30 | 2017-09-30 | Sol method prepares the low vanadium catalyst of multicomponent of pyromellitic acid dianhydride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108452819A (en) * | 2018-05-09 | 2018-08-28 | 常熟理工学院 | Prepare the low vanadium multi-component catalyst systems of equal acid anhydride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319580A (en) * | 2011-06-14 | 2012-01-18 | 常熟理工学院 | Catalyst and preparation method thereof |
| CN102626648A (en) * | 2012-03-20 | 2012-08-08 | 常熟市联邦化工有限公司 | Preparation of pyromellitic dianhydride (PMDA) multi-component oxide catalyst through catalytic gas phase oxidation method |
-
2017
- 2017-09-30 CN CN201710918712.5A patent/CN107715900A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319580A (en) * | 2011-06-14 | 2012-01-18 | 常熟理工学院 | Catalyst and preparation method thereof |
| CN102626648A (en) * | 2012-03-20 | 2012-08-08 | 常熟市联邦化工有限公司 | Preparation of pyromellitic dianhydride (PMDA) multi-component oxide catalyst through catalytic gas phase oxidation method |
Non-Patent Citations (1)
| Title |
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| 仓理等: "气相氧化法生产均苯四甲酸二酐催化剂进展", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108452819A (en) * | 2018-05-09 | 2018-08-28 | 常熟理工学院 | Prepare the low vanadium multi-component catalyst systems of equal acid anhydride |
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