CN109647471B - Catalyst for increasing yield of partial anhydride - Google Patents

Catalyst for increasing yield of partial anhydride Download PDF

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CN109647471B
CN109647471B CN201710946807.8A CN201710946807A CN109647471B CN 109647471 B CN109647471 B CN 109647471B CN 201710946807 A CN201710946807 A CN 201710946807A CN 109647471 B CN109647471 B CN 109647471B
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catalyst
oxalic acid
precursor
anhydride
alkaline earth
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CN109647471A (en
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顾龙勤
徐俊峰
陈亮
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a catalyst for improving the yield of a metanhydride, which mainly solves the problem that the yield of the metanhydride is not high due to poor activity and low selectivity to the metaanhydride of the catalyst in the prior art. The invention adopts the technical scheme that the vanadium oxide catalyst is adopted, and the active component of the catalyst comprises at least one of vanadium element, titanium element, alkaline earth metal element and IIIA group element, so that the technical problem is better solved, the occurrence of side reaction in the preparation process of the meta-anhydride is reduced, the effect on the oxidation reaction of the meta-trimethylbenzene is better, and the yield of the meta-anhydride is improved.

Description

Catalyst for increasing yield of partial anhydride
Technical Field
The invention relates to a catalyst for improving yield of partial anhydride, a preparation method thereof and a synthesis method of partial 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 is characterized in that the catalyst is a supported catalyst, and the active component of the supported catalyst comprises vanadium element, titanium element and at least one of alkaline earth metal element and IIIA group element; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring.
Preferably, the active component includes both vanadium element, titanium element, at least one element selected from alkaline earth metal elements, and at least one element selected from group iiia elements. In this case, the alkaline earth metal element and the IIIA group element have a synergistic effect in improving the yield of the partial anhydride.
In the above technical solution, the alkaline earth metal element is at least one selected from Be, Mg, Ca, Sr and Ba. More preferably Mg and Ca.
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 solutions, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, an alkaline earth metal element, and a group iiia element; for example, the active component includes V, Ti, Mg and Al, or V, Ti, Mg, Al and Ga, or V, Ti, Ca, Al and Ga, or V, Ti, Mg, Ca, Al and Ga.
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 alkaline earth metal element and IIIA 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 improving the yield of the partial anhydride, which is described in the technical scheme of one of the technical problems, 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 alkaline earth metal elements and IIIA group element compounds by using distilled water, and adding the mixture 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 alkaline earth metal element in the step (1) is preferably at least one selected from the group consisting of an alkaline earth metal oxide, an alkaline earth metal chloride, an alkaline earth metal nitrate, an alkaline earth metal sulfate and an alkaline earth metal acetate. More preferred are magnesium nitrate and calcium nitrate.
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 preferred are aluminum nitrate and gallium nitrate.
In the technical scheme, the preparation method for preparing the metaanhydride catalyst is characterized in that a precursor of the catalyst is put into a spraying machine, heated at 100-310 ℃ and 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 415-625 ℃, and the roasting time is 1-12 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: 1-32, and the reaction process conditions are as follows: the space velocity is 1100-10000 hr-1The reaction temperature is 310-620 ℃, 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 alkaline earth metal elements and IIIA group elements, which is beneficial to improving the performance of the catalyst, thereby improving the yield of the meta-anhydride.
The experimental result shows that the mole yield of the meta-anhydride prepared by the invention reaches 63.6%, and the good technical effect is achieved, especially when the active component in the catalyst simultaneously comprises vanadium element, titanium element, at least one element selected from alkaline earth metal elements and at least one element selected from IIIA group, the more prominent technical effect is achieved, and the catalyst can be used for the synthesis of the meta-anhydride. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
62g of oxalic acid and 210ml 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. 0.8 molar part of magnesium nitrate is dissolved in 51ml of distilled water and added to the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml of distilled water, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. Loading the catalyst precursorAnd (4) putting the mixture into a spraying machine, and uniformly spraying the mixture on the inert carrier silicon carbide. Roasting at 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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 2 ]
62g of oxalic acid and 210ml 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. 0.8 molar part of aluminum nitrate was dissolved in 51ml of distilled water, and the solution was added thereto, followed by further reaction at 60 ℃ for 1 hour. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 62.9 percent when the evaluation is carried out in a fixed bed reactor, the evaluation result is detailed in the table 1.
Comparative example 1
62g of oxalic acid and 210ml 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, continuously stirring to obtain an ammonium vanadyl oxalate solution, and continuously reacting for 1h at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is determined to be 59.7% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with the examples 1-2, the catalyst adopted by the invention has better performance and higher yield of the anhydride compared with the catalyst only containing V, Ti active components, wherein the catalyst contains V, Ti and Mg active components and V, Ti and Al active components.
[ example 3 ]
62g of oxalic acid and 210ml 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. 0.8 molar part of calcium nitrate is dissolved in 51ml of distilled water and added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 7 parts by mole of titanium tetrachloride into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.0% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
[ example 4 ]
62g of oxalic acid and 210ml 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. 0.8 molar part of calcium acetate is dissolved by 51ml of distilled water and then added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 7 parts by mole of titanium tetrachloride into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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.
[ example 5 ]
62g of oxalic acid and 210ml 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. After 0.8 parts by mole of magnesium sulfate was dissolved in 51ml of distilled water, the solution was added and the reaction was continued at 60 ℃ for 1 hour. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 62.9 percent when the evaluation is carried out in a fixed bed reactor, the evaluation result is detailed in the table 1.
[ example 6 ]
62g of oxalic acid and 210ml 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. 0.8 molar part of aluminum acetate is dissolved in 51ml of distilled water and added into the solution, and the reaction is continued for 1 hour at 60 ℃. Adding 7 parts by mole of titanium tetrachloride into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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 7 ]
62g of oxalic acid and 210ml 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. By distillation of 51mlDissolving 0.8 mol fraction of gallium sulfate in water, adding the solution, and continuously reacting for 1h at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.0% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
[ example 8 ]
62g of oxalic acid and 210ml 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. Dissolving 0.8 molar parts of gallium nitrate in 51ml of distilled water, adding the solution, and continuing to react for 1 hour at the temperature of 60 ℃. Adding 7 parts by mole of titanium tetrachloride into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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.
[ example 9 ]
62g of oxalic acid and 210ml 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. 0.4 mole parts of magnesium nitrate and 0.4 mole parts of aluminum nitrate were dissolved in 51ml of distilled water, and added to the solution, followed by further reaction at 60 ℃ for 1 hour. Adding 7 parts by mole of titanium dioxide into 21ml 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 the spray coater to be uniformSprayed on the silicon carbide inert carrier. Roasting at 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the meta-anhydride is 63.8% by evaluation in a fixed bed reactor, the evaluation results are shown in table 1.
Compared with the examples 1-2, the alkaline earth metal Mg element and the IIIA group Al element have better synergistic effect on improving the yield of the meta-anhydride.
[ example 10 ]
62g of oxalic acid and 210ml 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. 0.2 mole parts of magnesium nitrate, 0.2 mole parts of calcium nitrate and 0.4 mole parts of aluminum nitrate were dissolved in 51ml of distilled water, and then added to the solution, followed by continuing the reaction at 60 ℃ for 1 hour. Grinding 7 parts by mole of titanium dioxide with 21ml of distilled water, adding the ground titanium dioxide 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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.
In this example, it can be seen from comparison with example 9 that the alkaline earth metals Mg and Ca have a better synergistic effect with the other active components of the present invention in increasing the yield of the partial anhydride.
[ example 11 ]
62g of oxalic acid and 210ml 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. Dissolving 0.4 mole parts of calcium nitrate, 0.2 mole parts of aluminum nitrate and 0.2 mole parts of gallium nitrate in 51ml of distilled water, adding the solution into the solution, and continuously reacting at 60 DEG CAnd the time is 1 hour. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is measured to be 64.1 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
In this example, it can be seen that, compared to example 9, IIIA group Al and Ga have a better synergistic effect with other active components of the present invention in increasing the yield of the partial anhydride.
[ example 12 ]
62g of oxalic acid and 210ml 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. 0.4 mole parts of magnesium nitrate, 0.2 mole parts of aluminum nitrate and 0.2 mole parts of gallium nitrate are dissolved by 51ml of distilled water, added into the solution and continuously reacted for 1 hour at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the metaanhydride is measured to be 64.2 percent by evaluation in a fixed bed reactor, the evaluation result is detailed in table 1.
[ example 13 ]
62g of oxalic acid and 210ml 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. Dissolving 0.2 mole parts of magnesium nitrate, 0.2 mole parts of calcium nitrate, 0.2 mole parts of aluminum nitrate and 0.2 mole parts of gallium nitrate in 51ml of distilled waterAdding the mixture into the solution, and continuing the reaction for 1h at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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.
Comparing this example with examples 10 and 11, it can be seen that V, Ti, alkaline earth metals Mg and Ca, and IIIA group Al and Ga have very good synergistic effect in increasing the yield of the partial anhydride.
Comparative example 2
62g of oxalic acid and 210ml 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. 0.4 molar parts of manganese nitrate and 0.4 molar parts of cobalt nitrate are dissolved in 51ml of distilled water, added into the solution and reacted for 1 hour at 60 ℃. Adding 7 parts by mole of titanium dioxide into 21ml 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 560 ℃ in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is reacted at the temperature of 415 ℃ and the space velocity of 3150h-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 62.8%, and the evaluation results are detailed in table 1.
TABLE 1
Figure BDA0001431859540000091
Figure BDA0001431859540000101

Claims (7)

1. A method for improving the yield of the meta-anhydride takes pseudocumene, water vapor and air as raw materials, adopts a fixed bed reactor, and synthesizes the meta-anhydride in the presence of a catalyst; the catalyst is a supported catalyst, and the active components of the supported catalyst comprise vanadium element, titanium element and alkaline earth metal element, or vanadium element, titanium element, alkaline earth metal element and IIIA group element; 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; 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 alkaline earth metal element and IIIA group element in the catalyst is 1: (0.01-0.8).
2. The method according to claim 1, wherein the alkaline earth metal element is at least one selected from Be, Mg, Ca, Sr and Ba.
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 alkaline earth metal elements and IIIA group element compounds by using distilled water, and adding the mixture 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 100-310 ℃ to uniformly spray the precursor onto the support.
6. The method of claim 4, wherein the carrier coated with the catalyst precursor is calcined in a muffle furnace at a temperature of 415-625 ℃ for 1-12 hours.
7. The process of claim 1, wherein the volumetric ratio of mesitylene to steam fed is 1: (1-32), wherein the reaction process conditions are as follows: the space velocity is 1100-10000 hr-1The reaction temperature is 310-620 ℃, and the reaction pressure is normal pressure.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4849736A (en) * 1971-10-23 1973-07-13
CN104649885A (en) * 2013-11-19 2015-05-27 中国石油天然气股份有限公司 Method for preparing unsaturated acid from unsaturated aldehyde

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4849736A (en) * 1971-10-23 1973-07-13
CN104649885A (en) * 2013-11-19 2015-05-27 中国石油天然气股份有限公司 Method for preparing unsaturated acid from unsaturated aldehyde

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