CN110560111B - Catalyst for synthesizing meta-anhydride from pseudocumene - Google Patents
Catalyst for synthesizing 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 synthesizing meta-anhydride from pseudocumene, which mainly solves the problem of lower yield of the meta-anhydride in the oxidation reaction of the pseudocumene in the prior art, and the main reason is that the selectivity of a target product is poor due to poor performance of the catalyst. The invention adopts a technical scheme that a catalyst which takes vanadium and titanium elements as main catalytic elements, and the active components of the catalyst comprise vanadium elements, titanium elements, IIIA group elements and at least one of alkali metal elements and VA group elements. The scheme improves the catalyst performance, reduces the generation of byproducts in the oxidation reaction of the pseudocumene, and effectively solves the problem of low yield of the metanhydride.
Description
Technical Field
The invention relates to a catalyst for synthesizing 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 GE 1518613 researches V-Mo-Cu catalyst for gas phase oxidation reaction of unsym-trimethyl benzene, and obtains good catalytic effect. 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 synthesizing the meta-anhydride from the meta-trimethylbenzene, 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 synthesizing the meta-anhydride from the pseudocumene is characterized in that the catalyst is a supported catalyst taking vanadium and titanium as main catalytic elements, and the active components of the catalyst comprise vanadium, titanium, IIIA group elements and at least one of alkali metal elements and VA group elements; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring.
Preferably, the active component includes vanadium, titanium, a group iiia element, at least one element selected from alkali metal elements, and at least one element selected from group VA elements at the same time. At the moment, the five elements have synergistic effect on the aspect of improving the yield of the partial anhydride.
In the above technical solution, the group iiia element is at least one selected from Al, Ga, In and Tl. More preferably Al and Ga.
In the above technical solution, the alkali metal element is selected from at least one of Li, Na, K, Rb and Cs. More preferably Na and K.
In the above technical solution, the VA group element is at least one selected from P, Sb and Bi. More preferably P and Bi.
In the above technical solutions, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, a iiia group element, an alkali metal element, and a VA group element; for example, the active component includes V, Ti, Al, K and Bi, or V, Ti, Al, Na, K and P, or V, Ti, Al, Na, K, P and Bi.
In the technical scheme, the molar ratio of vanadium element, titanium element and IIIA group element in the catalyst is 1: (1-15): (0.1-5);
the molar ratio of vanadium element to the sum of alkali metal element and VA group element in the catalyst is 1: (0.01-1), more preferably 1: (0.02-0.8).
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst for synthesizing the metaanhydride 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; adding IIIA group elements, alkali metal elements and VA group element 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 onto a carrier, wherein the molar ratio of the precursor to the carrier is 1 (1-10), 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 group IIIA element compound in the step (1) is preferably at least one selected from alumina, aluminum nitrate, aluminum sulfate, aluminum acetate, gallium nitrate, gallium sulfate, gallium chloride and gallium acetate. More preferably aluminum nitrate or gallium acetate. The compound of the alkali metal element in the step (1) is preferably at least one selected from the group consisting of salts such as sodium nitrate, sodium sulfate, sodium acetate, potassium nitrate, potassium sulfate, and potassium acetate. More preferably potassium nitrate and sodium nitrate. The compound of the VA group element in the step (1) is preferably at least one selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, bismuth oxide, bismuth nitrate and bismuth sulfate. More preferred are ammonium dihydrogen phosphate and bismuth nitrate.
In the technical scheme, the preparation method of the catalyst for synthesizing the meta-anhydride from the pseudocumene is characterized in that a precursor of the catalyst is put into a spraying machine and is uniformly sprayed on a carrier after being heated at the temperature of 100-300 ℃.
In the technical scheme, the preparation method of the catalyst for synthesizing the meta-anhydride from the pseudocumene is characterized in that the carrier sprayed with the catalyst precursor is roasted in a muffle furnace, the roasting temperature is 400-600 ℃, and the roasting time is 1-10 h.
To solve the third technical problem, the technical scheme of the invention is as follows: the preparation method of 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: 1-30, and the reaction process conditions are as follows: the space velocity is 1000-10000 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, IIIA group element and at least one element selected from alkali metal element and iron series element, which is beneficial to improving the performance of the catalyst, thereby improving the yield of the metaanhydride.
The experimental result shows that the mole yield of the meta-anhydride prepared by the invention reaches 66.1%, and the good technical effect is achieved, especially when the active component in the catalyst simultaneously comprises vanadium element, titanium element, IIIA group element, at least one element selected from alkali metal elements and at least one element selected from iron series elements, the 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 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate and 0.4 mole fraction potassium nitrate were added to the solution and the reaction was continued at 60 ℃ for 1 hour. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.6 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 2 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate and 0.4 mole fraction ammonium dihydrogen phosphate are added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: the water vapor is equal to 0.05,the molar yield of the metaanhydride was found to be 64.5% when evaluated in a fixed bed reactor, the results of which are detailed in Table 1.
Comparative example 1
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mol fraction of aluminum nitrate is added into the solution, and the reaction is continued for 1h at 60 ℃. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the yield is 61.8%, the evaluation result is shown in table 1.
Compared with the examples 1-2, the catalyst adopted by the invention has better performance than that of a catalyst only containing V, Ti and Al active components and has higher yield of the partial anhydride, and the catalyst simultaneously contains V, Ti, Al and K active components and V, Ti, Al and P active components.
[ example 3 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate and 0.4 mole fraction sodium nitrate are added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 8 parts by mole of titanium dioxide into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: steam 0.05 in fixed bedThe mole yield of the metaanhydride was found to be 64.3% by evaluation in the reactor, and the results are detailed in Table 1.
[ example 4 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. Adding 4 mol fraction gallium acetate and 0.4 mol fraction sodium acetate into the solution, and continuing the reaction for 1h at 60 ℃. Adding 8 parts by mole of titanium dioxide into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.6 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 5 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. Adding 4 mol fraction gallium acetate and 0.4 mol fraction potassium sulfate into the solution, and continuing to react for 1h at 60 ℃. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is 64.4% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
[ example 6 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and prepared into oxalic acid after the oxalic acid is completely dissolvedAnd (3) solution. And adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 4 mol fraction of aluminum nitrate and 0.4 mol fraction of diammonium hydrogen phosphate into the solution, and continuing to react for 1 hour at 60 ℃. Adding 8 parts by mole of titanium dioxide into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.3 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 7 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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 4 mole fraction gallium acetate and 0.4 mole fraction bismuth nitrate into the solution, and continuing to react for 1h at 60 ℃. Adding 8 parts by mole of titanium dioxide into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.5 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 8 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. Adding 4 mole fraction gallium acetate and 0.4 mole fraction bismuth sulfate into the solution, and continuing to react for 1h at 60 ℃. Grinding 8 mol parts of titanium tetrachloride with 30ml of distilled water, addingAnd fully stirring the reaction system to prepare slurry liquid to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is 64.4% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
[ example 9 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate, 0.2 mole fraction potassium nitrate and 0.2 mole fraction ammonium dihydrogen phosphate were added to the solution and the reaction was continued at 60 ℃ for 1 h. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.3 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
Compared with the examples 1-2, the alkali metal K element and the VA group P element have better synergistic effect on improving the yield of the meta-anhydride.
[ example 10 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate, 0.1 mole fraction potassium nitrate, 0.1 mole fraction sodium nitrate and 0.2 mole fraction ammonium dihydrogen phosphate were added to the solution, and the reaction was continued at 60 ℃ for 1 hour. Adding 8 mol parts of titanium tetrachloride into 30ml of distilled water, grinding, adding into a reaction system,fully stirring to prepare slurry liquid to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is 65.5% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with example 9, it can be seen that the alkali metals K and Na have better synergistic effect with other active components of the invention in increasing the yield of the partial anhydride.
[ example 11 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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 4 mole fraction aluminum nitrate, 0.2 mole fraction potassium nitrate, 0.1 mole fraction ammonium dihydrogen phosphate and 0.1 mole fraction bismuth nitrate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is 65.4% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with example 9, it can be seen that the elements P and Bi in the VA group and other active components of the invention have better synergistic effect on increasing the yield of the partial anhydride.
[ example 12 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. By mixing 4 moles ofAdding aluminum nitrate with mole fraction, sodium nitrate with 0.2 mole fraction, ammonium dihydrogen phosphate with 0.1 mole fraction and bismuth nitrate with 0.1 mole fraction into the solution, and continuing to react for 1h at 60 ℃. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is 65.6 percent, the evaluation result is detailed in table 1.
[ example 13 ]
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, 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. 4 mole fraction aluminum nitrate, 0.1 mole fraction potassium nitrate, 0.1 mole fraction sodium nitrate, 0.1 mole fraction ammonium dihydrogen phosphate and 0.1 mole fraction bismuth nitrate were added to the solution, and the reaction was continued at 60 ℃ for 1 hour. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is determined to be 66.1% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with examples 10 and 11, V, Ti, IIIA group Al, alkali metals K and Na, and VA group P and Bi have very good synergistic effect on improving the yield of the partial anhydride.
Comparative example 2
50g of oxalic acid and 180ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding 1 mol part of vanadium pentoxide into the mixtureAnd continuously stirring the solution in the prepared oxalic acid solution to obtain the ammonium vanadyl oxalate solution. Adding 0.2 mole fraction of manganese nitrate and 0.2 mole fraction of cobalt nitrate into the solution, and continuing to react for 1h at 60 ℃. Adding 8 parts by mole of titanium tetrachloride into 30ml of distilled water, 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 550 ℃ 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 3000 hours-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.
TABLE 1
Claims (6)
1. The catalyst for synthesizing the meta-anhydride from the pseudocumene is characterized in that the catalyst is a supported catalyst taking vanadium and titanium as main catalytic elements, and the active components of the catalyst comprise vanadium, titanium, IIIA group elements, alkali metal elements and VA group elements; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring; wherein the IIIA group element is selected from at least one of Al, Ga, In and Tl, and the VA group element is selected from at least one of P, Sb and Bi; the molar ratio of vanadium element, titanium element and IIIA group element in the catalyst is 1: (1-15): (0.1-5), wherein the molar ratio of the vanadium element to the sum of the alkali metal element and the VA group element in the catalyst is 1: (0.01-1).
2. The catalyst for synthesizing a meta anhydride from pseudocumene according to claim 1, wherein the alkali metal element is at least one selected from the group consisting of Li, Na, K, Rb and Cs.
3. The process for preparing a catalyst for the synthesis of meta-anhydride from meta-trimethylbenzene as claimed in any of claims 1 to 2, 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; adding IIIA group elements, alkali metal elements and VA group element 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 catalyst precursor;
(3) spraying a catalyst precursor onto a carrier, wherein the molar ratio of the catalyst precursor to the carrier is 1 (1-10), and roasting to obtain the catalyst.
4. The method as claimed in claim 3, wherein the catalyst precursor is loaded into a spray coater, and heated at 100-300 ℃ and then uniformly sprayed on the carrier.
5. The method as claimed in claim 3, wherein the carrier coated with the catalyst precursor is calcined in a muffle furnace at 400-600 deg.C for 1-10 h.
6. A method for synthesizing meta anhydride from pseudocumene, in the presence of the catalyst of any one of claims 1-2, using pseudocumene, steam and air as raw materials to synthesize the meta anhydride, and adopting a fixed bed reactor, wherein the volume ratio of the pseudocumene to the steam is 1: (1-30), and the reaction process conditions are as follows: the space velocity is 1000-10000 hr-1The reaction temperature is 300-600 ℃, and the reaction pressure is normal pressure.
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Citations (9)
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