CN109647468B - Catalyst for preparing meta-anhydride from pseudocumene - Google Patents
Catalyst for preparing meta-anhydride from pseudocumene Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
Abstract
The invention relates to a catalyst for preparing meta-anhydride from pseudocumene, which mainly solves the problem of low yield of the meta-anhydride caused by more byproducts generated in the process of preparing the meta-anhydride from the pseudocumene in the prior art. The invention adopts a supported oxide catalyst, the active component of the catalyst comprises vanadium element, titanium element and at least one of IVA group element and VIB group element, the technical scheme that the carrier adopts at least one of silicon carbide, ceramic ring and alpha-alumina is adopted, the technical problem is better solved, the catalyst has better catalytic performance for preparing the meta-anhydride from the meta-trimethylbenzene, the generation of byproducts is reduced, and the yield of the meta-anhydride is improved.
Description
Technical Field
The invention relates to a catalyst for preparing meta-anhydride from pseudocumene, a preparation method thereof and a synthesis method of the meta-anhydride.
Technical Field
Trimellitic anhydride (TMA), also known as 1, 2, 4-benzene tricarboxylic anhydride for short, is an important chemical raw material and a high value-added intermediate, and is widely applied to the production industries of high-temperature-resistant plasticizers, polyester resins, polyester epoxy powder coatings, insulating paint, water-soluble alkyd resins, lubricating oil, printing ink, adhesives and the like. The prepared resin material has excellent point insulation performance, high temperature resistance and mechanical performance, and is widely applied to the industrial fields of electronics, aerospace, electromechanics and the like.
At present, the production of the meta-anhydride in the world is mainly based on the pseudocumene liquid-phase oxidation technology represented by the United states and Japan, and accounts for about 70 percent of the total production in the world. The process takes pseudocumene as a raw material, takes Co-Mn-Br as a catalyst in an acetic acid medium, and prepares the meta-anhydride by air oxidation. The process has high yield of the meta-anhydride, but has long reaction flow, serious corrosion to equipment and large investment, and can bring pressure to the production cost. The gas phase oxidation method is a method for directly generating the meta-anhydride by using the air to carry out one-step oxidation by using the pseudocumene as a raw material under the action of a catalyst. Compared with the liquid phase oxidation method, the method avoids the problems, has low production cost and is the most ideal method for producing the meta-anhydride.
At present, the gas phase oxidation method causes high international attention, and research work of the method is developed in many times. German GE1518613 researches V-Mo-Cu catalyst for gas phase oxidation of pseudocumene, and obtains good catalytic effect. JP48-49736 studies a V-Ti catalyst for the catalytic oxidation of mesitylene with an oxygen-containing gas. CN 105498817A researches a V-Ti-Mn-Co metal oxide and heteropoly acid composite catalyst, and the molar yield can reach 56.2%. Compared with the prior art at home and abroad, the prior art at home is still imperfect, has low construction rate and can not meet the market demand of the domestic meta-anhydride. Therefore, it is necessary to improve the selectivity of the catalyst to the partial anhydride by changing the preparation method of the catalyst.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low yield of the meta-anhydride in the prior art, and the invention provides a catalyst for preparing the meta-anhydride, which has the characteristic of high yield of the meta-anhydride.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The present invention is also directed to a method for preparing a meta-anhydride, which is one of the technical problems to be solved.
In order to solve one of the above technical problems, the technical solution disclosed by the present invention is: the catalyst for preparing the partial anhydride from the pseudocumene is characterized by being a supported catalyst, wherein the active component of the supported catalyst comprises vanadium element, titanium element and at least one of IVA group element and VIB group element; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring.
Preferably, the active component comprises simultaneously vanadium, titanium, at least one element selected from group IVA elements and at least one element selected from group VIB elements. At the moment, the IVA group metal elements and VIB group metal elements have synergistic effect on the aspect of improving the yield of the partial anhydride.
In the above technical solution, the group IVA element is selected from at least one of Ge, Sn, and Pb. More preferably Ge and Sn.
In the above technical solution, the VIB element is selected from at least one of Cr, Mo, and W. More preferably Cr and Mo.
In the above technical solution, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, an IVA group element, and a VIB group element; for example, the active component includes V, Ti, Ge and Mo, or V, Ti, Ge, Sn and Mo, or V, Ti, Ge, Mo and Cr, or V, Ti, Ge, Sn, Cr and Mo.
In the technical scheme, the molar ratio of the vanadium element to the titanium element in the catalyst is 1: (1-15), more preferably 1: (2-10); the molar ratio of vanadium element to the sum of IVA group element and VIB group element in the catalyst is 1: (0.01-0.8), more preferably 1: (0.02-0.8).
The technical scheme is characterized in that the molar ratio of the active component to the carrier in the supported catalyst is 1 (1-10).
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst for preparing the metanhydride from the pseudocumene comprises the following steps:
(1) dissolving oxalic acid in distilled water to obtain an oxalic acid solution; adding a vanadium source into an oxalic acid solution to obtain a mixed solution; dissolving the IVA group element and VIB group element compounds by using distilled water, and adding the dissolved compounds into a reaction system;
(2) adding water into a titanium source, grinding, slowly dropwise adding the ground titanium source into a reaction system, and fully stirring to prepare slurry to obtain a precursor;
(3) spraying the precursor on a carrier, and roasting to obtain the catalyst.
In the above technical solution, the vanadium source in step (1) is preferably at least one selected from vanadium oxide, metavanadate, orthovanadate and vanadium chloride. The titanium source in the step (2) is preferably at least one of titanium dioxide and titanium tetrachloride. The compound of the group IVA element in the step (1) is preferably at least one selected from the group consisting of germanium oxide, germanium halide, organogermanide, tin oxide, tin sulfide, tin halide and inorganic salt of tin. More preferred are sodium metagermanate and tin sulfate.
The group VIB element compound in step (1) is preferably at least one selected from chromium oxide, chromium chloride, chromium salt, chromate, molybdenum oxide, molybdenum chloride, molybdenum salt and molybdate. More preferred are ammonium molybdate and chromium chloride.
In the technical scheme, the preparation method for the catalyst for preparing the metaanhydride from the pseudocumene is characterized in that a precursor of the catalyst is put into a spraying machine, heated at 220-500 ℃ and then uniformly sprayed on a carrier.
In the technical scheme, the preparation method for the catalyst for preparing the metaanhydride is characterized in that the carrier sprayed with the catalyst precursor is roasted in a muffle furnace, the roasting temperature is 220-620 ℃, and the roasting time is 1-11 h.
To solve the third technical problem, the technical scheme of the invention is as follows: the method for preparing the meta-anhydride takes durene, water vapor and air as raw materials and adopts a fixed bed reactor to synthesize the meta-anhydride in the presence of a catalyst.
The reaction process conditions in the technical scheme are as follows: the volume ratio of the pseudocumene to the steam is 1: 1-22, and the reaction process conditions are as follows: the space velocity is 1200-10000 hr-1The reaction temperature is 300-600 ℃, and the reaction pressure is normal pressure.
Compared with the prior art, the key point of the invention is that the active component of the catalyst comprises a certain amount of vanadium element, titanium element and at least one element selected from IVA group element and VIB group element, which is beneficial to improving the performance of the catalyst, thereby improving the yield of the meta-anhydride.
The experimental result shows that the molar yield of the meta-anhydride prepared by the invention reaches 63.0%, and a better technical effect is achieved, particularly when the active component in the catalyst simultaneously comprises vanadium element, titanium element, at least one element selected from IVA group elements and at least one element selected from VIB group elements, a more prominent technical effect is achieved, and the catalyst can be used for synthesizing the meta-anhydride. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 mole part of sodium metagermanate is dissolved in 50ml of distilled water and added into the solution, and the reaction is continued for 1 hour at 60 ℃. Grinding 4 mol parts of titanium dioxide by adding 20ml of distilled waterAdding the reaction system, fully stirring to prepare slurry liquid, and obtaining the precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 62.0 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 2 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of ammonium molybdate is dissolved by 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the yield is 61.9%, the evaluation result is shown in table 1.
Comparative example 1
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: steam of 0.05, evaluated in a fixed bed reactor, and the molar yield of the metaanhydride is determined to be59.2%, and the evaluation results thereof are detailed in Table 1.
Compared with the examples 1-2, the catalyst adopted by the invention has the advantages that the performance of the catalyst containing V, Ti and Ge active components and V, Ti and Mo active components is better than that of the catalyst containing V, Ti active components, and the yield of the anhydride is higher.
[ example 3 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of tin sulfate was dissolved in 50ml of distilled water and added to the solution, and the reaction was continued at 60 ℃ for 1 hour. Adding 20ml of distilled water into 4 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is measured in a fixed bed reactor, the yield is 62.3 percent, and the evaluation result is detailed in table 1.
[ example 4 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. After 0.4 molar part of germanium sulfide was dissolved in 50ml of distilled water, the solution was added and the reaction was continued at 60 ℃ for 1 hour. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: steam of 0.05, and the mole yield of the partial anhydride is 62.1 percent when evaluated in a fixed bed reactorThe evaluation results are shown in Table 1.
[ example 5 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of tin chloride was dissolved in 50ml of distilled water and added to the solution, and the reaction was continued at 60 ℃ for 1 hour. Adding 20ml of distilled water into 4 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is measured in a fixed bed reactor, the mole yield of the partial anhydride is 62.2 percent, and the evaluation result is detailed in table 1.
[ example 6 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of molybdenum chloride is dissolved by 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 62.0 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 7 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the preparedAnd continuously stirring the oxalic acid solution to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of chromium sulfate is dissolved by 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is measured in a fixed bed reactor, the yield is 62.3 percent, and the evaluation result is detailed in table 1.
[ example 8 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.4 molar part of chromium chloride is dissolved by 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is measured in a fixed bed reactor, the mole yield of the partial anhydride is 62.1 percent, and the evaluation result is detailed in table 1.
[ example 9 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.2 mole parts of sodium metagermanate and 0.2 mole parts of ammonium molybdate are dissolved in 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, fully stirring to prepare slurryAnd (6) obtaining a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the yield is 62.2%, the evaluation result is shown in table 1.
Compared with the examples 1-2, the example shows that the group IVA Ge element and the group VIB Mo element have better synergistic effect on improving the yield of the partial anhydride.
[ example 10 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.1 mole part of sodium metagermanate, 0.1 mole part of tin sulfate and 0.2 mole part of ammonium molybdate are dissolved in 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.4% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
Compared with example 9, the example shows that the elements of the IVA group Ge and Sn have better synergistic effect on improving the yield of the partial anhydride with other active components of the invention.
[ example 11 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 0.1 mole part of sodium metagermanate and 0.1 mole part of sulfuric acid into 50ml of distilled waterTin and 0.2 mol portion of chromium chloride are dissolved and added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.2% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
[ example 12 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.2 mole parts of sodium metagermanate, 0.1 mole parts of ammonium molybdate and 0.1 mole parts of chromium chloride are dissolved by 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.3% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
Compared with example 9, the present example shows that the elements of group VIB Mo and Cr have better synergistic effect with other active components of the present invention in increasing the yield of the partial anhydride.
[ example 13 ]
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.1 molar part of sodium metagermanate is added into 50ml of distilled water0.1 mol portion of tin sulfate, 0.1 mol portion of ammonium molybdate and 0.1 mol portion of chromium chloride are dissolved and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.9% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
Compared with examples 10 and 11, the present example shows that the elements of Ge and Sn in groups V, Ti and IVA and the elements of Mo and Cr in group VIB have very good synergistic effect on the improvement of the yield of the partial anhydride.
Comparative example 2
64g of oxalic acid and 195ml of distilled water are weighed in a flask, stirred and heated to 82 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 0.2 mole parts of manganese nitrate and 0.2 mole parts of cobalt nitrate are dissolved in 50ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 20ml of distilled water into 4 molar parts of titanium dioxide, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 540 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 400 ℃ and the space velocity of 3400h-1The following, pseudocumene: when the steam is 0.05 and the yield is 61.2%, the evaluation result is shown in table 1.
TABLE 1
Claims (7)
1. A method for preparing the meta-anhydride, take meta-trimethylbenzene, water vapor, air as raw materials, adopt the fixed bed reactor, synthesize the meta-anhydride under the existence of catalyst; the catalyst is a supported catalyst, and the active components of the supported catalyst comprise vanadium, titanium and IVA group elements, or vanadium, titanium, IVA group elements and VIB group elements; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring;
the group IVA element is selected from at least one of Ge, Sn and Pb; the molar ratio of the vanadium element to the titanium element in the catalyst is 1: (1-15); the molar ratio of vanadium element to the sum of IVA group element and VIB group element in the catalyst is 1: (0.01-0.8).
2. The method according to claim 1, wherein the VIB element is at least one selected from Cr, Mo and W.
3. The process of claim 1, wherein the molar ratio of active component to support in the supported catalyst is from 1 (1) to 10.
4. A process according to any one of claims 1 to 3, wherein the catalyst is prepared by a process comprising the steps of:
(1) dissolving oxalic acid in distilled water to obtain an oxalic acid solution; adding a vanadium source into an oxalic acid solution to obtain a mixed solution; dissolving the IVA group element and VIB group element compounds by using distilled water, and adding the dissolved compounds into a reaction system;
(2) adding water into a titanium source, grinding, slowly dropwise adding the ground titanium source into a reaction system, and fully stirring to prepare slurry to obtain a precursor;
(3) spraying the precursor on a carrier, and roasting to obtain the catalyst.
5. The method of claim 4, wherein the precursor of the catalyst is charged into a spray coater and heated at 220-500 ℃ to uniformly spray the precursor onto the support.
6. The method of claim 4, wherein the support coated with the catalyst precursor is calcined in a muffle furnace at a temperature of 220-620 ℃ for a time of 1-11 hours.
7. The process of claim 1, wherein the volumetric ratio of mesitylene to steam fed is 1: (1-22), and the reaction process conditions are as follows: the space velocity is 1200-10000 hr-1The reaction temperature is 300-600 ℃, and the reaction pressure is normal pressure.
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| CN1803285A (en) * | 2005-12-27 | 2006-07-19 | 张荣成 | Selective ammoxidation catalyst for multiple methyl arene, its preparation method and uses |
| CN102319580A (en) * | 2011-06-14 | 2012-01-18 | 常熟理工学院 | Catalyst and preparation method thereof |
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| CN1803285A (en) * | 2005-12-27 | 2006-07-19 | 张荣成 | Selective ammoxidation catalyst for multiple methyl arene, its preparation method and uses |
| CN102319580A (en) * | 2011-06-14 | 2012-01-18 | 常熟理工学院 | Catalyst and preparation method thereof |
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