CN110560110B - Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene - Google Patents
Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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Abstract
The invention relates to a catalyst for synthesizing meta-anhydride by oxidizing pseudocumene, which mainly solves the problem of lower yield in the process of synthesizing the meta-anhydride by oxidizing the pseudocumene in the prior art. This is mainly due to the poor catalyst performance, which leads to poor selectivity for the partial anhydride. The invention adopts a technical scheme that a supported 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 IIB group elements and nonmetal elements. The catalyst effectively reduces the generation of byproducts in the oxidation reaction of the pseudocumene and effectively improves the yield of the metanhydride.
Description
Technical Field
The invention relates to a catalyst for synthesizing meta-anhydride by oxidizing 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 homoanhydride 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 partial anhydride in the prior art, and the invention provides a catalyst for synthesizing the partial anhydride by oxidizing the partial trimethylbenzene, which has the characteristic of high yield of the partial 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 IIB group elements and nonmetal 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 a group IIB element, and at least one element selected from a non-metallic element 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 scheme, the group IIB element is selected from at least one of Zn, Cd and Hg. More preferably Zn and Cd.
In the above technical solution, the nonmetal element is at least one selected from the group consisting of B, Si, As, Te and Se. More preferably B, Te.
In the above technical solution, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, a iiia group element, a iib group element, and a nonmetal element; for example, the active component includes V, Ti, Al, Zn and B, or V, Ti, Al, Zn, B and Te, or V, Ti, Al, Ga, Zn, B and Te.
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 IIB group element and nonmetal element in the catalyst is 1: (0.01-1), more preferably 1: (0.01-0.9).
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 partial anhydride by oxidizing 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
To a mixed solution; adding IIIA group elements, IIB group elements and nonmetal 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, fully stirring the mixture to prepare slurry to obtain the titanium-containing catalyst
Obtaining 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
To 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 group IIB element in the step (1) is preferably at least one of zinc oxide, zinc sulfate, zinc nitrate, zinc acetate, other zinc salts, cadmium oxide, cadmium nitrate, cadmium sulfate, cadmium acetate and other cadmium salts. More preferably zinc nitrate and cadmium nitrate. The compound of the nonmetallic element in the step (1) is preferably at least one of boric acid, ammonium pentaborate, borate, telluric acid, tellurium oxide and tellurate. More preferred are ammonium pentaborate and ammonium tellurate.
In the technical scheme, the preparation method of the catalyst for synthesizing the meta-anhydride by oxidizing 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 120-310 ℃.
In the technical scheme, the preparation method of the catalyst for synthesizing the meta-anhydride by oxidizing the pseudocumene is characterized in that the carrier sprayed with the catalyst precursor is roasted in a muffle furnace, the roasting temperature is 420-610 ℃, and the roasting time is 1-11 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 IIB group element and nonmetal 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 66.2%, 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 IIB group element and at least one element selected from nonmetal elements, the more outstanding 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 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 2 mole fraction of aluminum nitrate and 0.4 mole fraction of zinc nitrate are added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 6 molar parts 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 measured in a fixed bed reactor, the yield is 64.8 percent, and the evaluation result is detailed in table 1.
[ example 2 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 2 mole fraction of aluminum nitrate and 0.4 mole fraction of ammonium pentaborate are added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 6 molar parts of titanium tetrachloride into 30ml of distilled water, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. Loading the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on inert carrier carbonOn the silicon oxide. 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.
Comparative example 1
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. The reaction is continued for 1h at 60 ℃ by adding 2 mole fraction of aluminum nitrate into the solution. Adding 6 molar parts 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 61.9%, 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 higher yield of the partial anhydride, and contains V, Ti, Al and Zn active components simultaneously and V, Ti, Al and B active components simultaneously.
[ example 3 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. 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 2 mole fraction of aluminum nitrate and 0.4 mole fraction of cadmium nitrate into the solution, and continuing to react for 1 hour at 60 ℃. Adding 30ml of distilled water into 6 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 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 measured in a fixed bed reactor, the yield is 64.7 percent, and the evaluation result is detailed in table 1.
[ example 4 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. 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 2 mole fraction gallium acetate and 0.4 mole fraction zinc acetate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 30ml of distilled water into 6 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 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 5 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. 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 2 mole fraction gallium acetate and 0.4 mole fraction cadmium sulfate into the solution, and continuing to react for 1h at 60 ℃. Adding 6 molar parts 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 measured in a fixed bed reactor, the yield is 64.8 percent, and the evaluation result is detailed in table 1.
[ example 6 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. 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 2 mole fraction aluminum nitrate and 0.4 mole fraction nitroboric acid into the solution, and continuing the reaction for 1h at 60 ℃. Adding 30ml of distilled water into 6 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 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 measured in a fixed bed reactor, the yield is 64.7 percent, and the evaluation result is detailed in table 1.
[ example 7 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 2 mole fraction gallium acetate and 0.4 mole fraction ammonium tellurate into the solution, and continuing to react for 1h at 60 ℃. Adding 30ml of distilled water into 6 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 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 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain vanadyl oxalateAmmonium solution. Adding 2 mole fraction gallium acetate and 0.4 mole fraction telluric acid into the solution, and continuing to react for 1h at 60 ℃. Adding 6 molar parts 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 9 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 2 mole fraction of aluminum nitrate, 0.2 mole fraction of zinc nitrate and 0.2 mole fraction of ammonium pentaborate into the solution, and continuing the reaction at 60 ℃ for 1 hour. Adding 6 molar parts 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 65.1 percent, the evaluation result is detailed in table 1.
Compared with the examples 1-2, the group IIB Zn element and the nonmetal P element have better synergistic effect on improving the yield of the meta-anhydride.
[ example 10 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. 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 2 mole fractions of aluminum nitrate, 0.1 mole fraction of zinc nitrate and 0.1 mole fraction of zinc nitrateAdding fractional cadmium nitrate and 0.2 mole fraction ammonium pentaborate into the solution, and continuing to react for 1h at 60 ℃. Adding 6 molar parts 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.
Compared with example 9, the example shows that the elements of group IIB Zn and Cd and other active components of the invention have better synergistic effect on improving the yield of the meta-anhydride.
[ example 11 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 2 mole fraction aluminum nitrate, 0.2 mole fraction zinc nitrate, 0.1 mole fraction ammonium pentaborate and 0.1 mole fraction ammonium tellurate into the solution, and continuing to react for 1h at 60 ℃. Adding 6 molar parts 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 65.7 percent, the evaluation result is detailed in table 1.
Compared with example 9, it can be seen that the non-metal elements B and Te have better synergistic effect with other active components of the invention in increasing yield of the anhydride.
[ example 12 ]
52g of oxalic acid and 185ml of distilled water are weighed into a flask, stirred and heated to 85 ℃ until oxalic acid is obtainedAfter all the components are dissolved, oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 2 mole fraction aluminum nitrate, 0.1 mole fraction cadmium nitrate and 0.2 mole fraction ammonium pentaborate into the solution, and continuously reacting for 1h at 60 ℃. Adding 6 molar parts 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 65.5% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
[ example 13 ]
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 2 mole fraction aluminum nitrate, 0.1 mole fraction zinc nitrate, 0.1 mole fraction cadmium nitrate, 0.1 mole fraction ammonium pentaborate and 0.1 mole fraction ammonium tellurate into the solution, and continuing to react for 1h at 60 ℃. Adding 6 molar parts 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 66.2% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with the examples 10 and 11, the embodiment shows that V, Ti, IIIA group Al, IIB group Zn and Cd elements, nonmetal B and Te elements have good synergistic effect on improving the yield of the partial anhydride.
Comparative example 2
52g of oxalic acid and 185ml of distilled water are weighed in a flask, stirred and heated to 85 ℃, and after the oxalic acid is completely dissolved, an oxalic acid solution is prepared. Adding 1 mol part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 0.2 mole fraction manganese nitrate and 0.2 mole fraction cobalt nitrate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 6 molar parts 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 63.1% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
TABLE 1
Claims (5)
1. The catalyst for synthesizing the meta-anhydride by oxidizing 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, IIB group elements and nonmetal elements; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring;
wherein the nonmetal element is selected from at least one of B, Si, As and Te, the IIIA group element is selected from at least one of Al, Ga, In and Tl, and the IIB group element is selected from at least one of Zn, Cd and Hg; 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 IIB group element and the nonmetal element in the catalyst is 1: (0.01-1).
2. The method for preparing the catalyst for synthesizing the partial anhydride by oxidizing the pseudocumene according to claim 1, comprising 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, IIB group elements and nonmetal 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.
3. The method as claimed in claim 2, wherein the catalyst precursor is loaded into a spraying machine, heated at 120-310 ℃ and uniformly sprayed on the carrier.
4. The method as claimed in claim 2, wherein the carrier coated with the catalyst precursor is calcined in a muffle furnace at 420-610 ℃ for 1-11 h.
5. A method for synthesizing the meta anhydride by oxidizing the pseudocumene, which takes the pseudocumene, the water vapor and the air as raw materials to synthesize the meta anhydride in the presence of the catalyst of claim 1, and adopts a fixed bed reactor, wherein the feeding volume ratio of the pseudocumene to the water vapor 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.
Priority Applications (1)
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