CN110560115A - Catalyst for synthesizing trimellitic anhydride - Google Patents
Catalyst for synthesizing trimellitic anhydride Download PDFInfo
- Publication number
- CN110560115A CN110560115A CN201810566776.8A CN201810566776A CN110560115A CN 110560115 A CN110560115 A CN 110560115A CN 201810566776 A CN201810566776 A CN 201810566776A CN 110560115 A CN110560115 A CN 110560115A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxalic acid
- precursor
- trimellitic anhydride
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing trimellitic anhydride, which mainly solves the problems of poor performance of the catalyst for the reaction for synthesizing trimellitic anhydride, more side reactions and lower yield of the trimellitic anhydride in the prior art. The invention adopts a supported catalyst, the active component of the catalyst comprises vanadium element, titanium element, iron series metal element and at least one of lanthanide series metal element and IIB group element, and the carrier is at least one of inert silicon carbide, alpha-alumina or ceramic ring. The scheme improves the performance of the catalyst for synthesizing the trimellitic anhydride and effectively improves the yield of the trimellitic anhydride.
Description
Technical Field
The invention relates to a catalyst for synthesizing trimellitic anhydride, a preparation method thereof and a synthesis method of the trimellitic 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. CN105498817A 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 trimellitic anhydride in the prior art, and the catalyst for synthesizing the trimellitic anhydride has the characteristic of high yield of the trimellitic 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 has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for synthesizing trimellitic anhydride, which is capable of solving the above-mentioned problems.
In order to solve one of the above technical problems, the technical solution disclosed by the present invention is: the catalyst for synthesizing trimellitic anhydride 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, iron metal and at least one of lanthanide metal and IIB group element; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring.
Preferably, the active component comprises simultaneously vanadium, titanium, iron-based metal, at least one element selected from the lanthanide series of metal elements and at least one element selected from the group iib elements. 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 iron-based element is selected from at least one of Fe, Co and Ni. Fe and Ni are preferred.
in the above technical solution, the lanthanide is selected from at least one of La, Ce, Pr, Nd, Sm, and Eu. More preferably La and Ce.
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 solutions, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, an iron-based metal element, a lanthanide-based metal element, and a group iib element; for example, the active component includes V, Ti, Fe, La and Zn, or V, Ti, Fe, La, Zn and Cd, or V, Ti, Fe, La, Ce, Zn and Cd.
In the technical scheme, the molar ratio of the vanadium element, the titanium element and the iron-based metal element in the catalyst is 1: (1-15): (0.1-5);
The molar ratio of vanadium element to the sum of lanthanide metal element and group IIB element in the catalyst is 1: (0.01-1), more preferably 1: (0.09-0.8).
To solve the second technical problem, the technical solution of the present invention is as follows: the process for the preparation of the catalyst for the synthesis of trimellitic anhydride described in the technical solution to one of the above technical problems comprises 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 iron series metal elements, lanthanide series metal elements and IIB 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 iron-based element in step (1) is preferably at least one of metal salts such as iron oxide, iron chloride, iron nitrate, iron sulfate, iron acetate, cobalt oxide, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel oxide, nickel nitrate, nickel sulfate, and nickel acetate. More preferred are iron nitrate and nickel nitrate. The lanthanide element in the step (1) is preferably at least one selected from lanthanum oxide, lanthanum chloride, lanthanum nitrate, lanthanum sulfate, lanthanum acetate, cerium oxide, cerium nitrate, cerium sulfate and cerium acetate. Lanthanum nitrate and cerium nitrate are more preferred. 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 preferred are zinc nitrate and cadmium nitrate.
In the technical scheme, the preparation method of the catalyst for synthesizing trimellitic anhydride is characterized in that a precursor of the catalyst is loaded into a spraying machine, and the precursor is uniformly sprayed on a carrier after being heated at 124-353 ℃.
In the technical scheme, the preparation method of the catalyst for synthesizing and producing trimellitic anhydride is characterized in that the carrier sprayed with the catalyst precursor is roasted in a muffle furnace, the roasting temperature is 413-612 ℃, and the roasting time is 2-12 h.
To solve the third technical problem, the technical scheme of the invention is as follows: the method for synthesizing trimellitic anhydride takes durene, water vapor and air as raw materials, adopts a fixed bed reactor, and synthesizes the trimellitic anhydride in the presence of a catalyst.
Reaction process in the technical schemethe conditions were 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, iron series metal element and at least one element selected from lanthanide series metal element and IIB group element, which is beneficial to improving the performance of the catalyst, thereby improving the yield of the anhydride.
The experimental result shows that the mole yield of the meta-anhydride prepared by the invention reaches 68.2%, and the good technical effect is achieved, especially when the active component in the catalyst simultaneously comprises vanadium element, titanium element, iron series metal element, at least one element selected from lanthanide series metal element and at least one element selected from IIB group element, 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 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction ferric nitrate and 0.4 mole fraction lanthanum nitrate into the solution, and continuing the reaction for 1h at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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.
[ example 2 ]
61g of oxalic acid and 196ml of distilled water are weighed into a flask, stirred and heated to 84 ℃ until the temperature is up toAfter 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 3 mole fraction ferric nitrate and 0.4 mole fraction zinc nitrate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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.
Comparative example 1
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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. 3 mol fraction ferric nitrate is added into the solution, and the reaction is continued for 1h at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 62.0 percent by evaluation in a fixed bed reactor, the evaluation result is detailed 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 Fe active components and containing V, Ti, Fe and Zn active components, and the yield of the meta-anhydride is higher.
[ example 3 ]
61g of oxalic acid and 196ml of distilled water are weighed into a flask, stirred and heated to 84 ℃ until oxalic acid is obtainedAfter all the components are dissolved, 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 3 mole fraction nickel nitrate and 0.4 mole fraction cerium nitrate into the solution, and continuing the reaction for 1h at 60 ℃. Adding 35ml of distilled water into 8 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 572 deg.c 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 66.0% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
[ example 4 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction nickel nitrate and 0.4 mole fraction lanthanum sulfate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 35ml of distilled water into 8 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 572 deg.c 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.
[ example 5 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction ferric nitrate and 0.4 mole fraction cerous sulfate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 35 to 8 mol portions of titanium tetrachlorideGrinding ml of distilled water, adding the ground distilled water 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 572 deg.c 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 65.9 percent, the evaluation result is detailed in table 1.
[ example 6 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction nickel nitrate and 0.4 mole fraction zinc acetate into the solution, and continuing the reaction at 60 ℃ for 1 h. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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.
[ example 7 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction nickel nitrate and 0.4 mole fraction cadmium nitrate into the solution, and continuing to react for 1h at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is at the reaction temperature of 400 ℃ and the space velocity3000h-1The following, pseudocumene: when the steam is 0.05 and the mole yield of the partial anhydride is determined to be 66.0% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
[ example 8 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction ferric nitrate and 0.4 mole fraction cadmium acetate into the solution, and continuing to react for 1h at 60 ℃. Adding 35ml of distilled water into 8 molar parts of titanium tetrachloride, grinding, adding into a reaction system, and fully stirring to prepare slurry to obtain a precursor. The catalyst precursor is loaded into a spraying machine and evenly sprayed on the inert carrier silicon carbide. Roasting at 572 deg.c 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.
[ example 9 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fractions of ferric nitrate, 0.2 mole fraction of lanthanum nitrate and 0.2 mole fraction of zinc nitrate into the solution, and continuing the reaction at 60 ℃ for 1 hour. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 66.9% by evaluation in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with the examples 1-2, the lanthanide La element and the IIB Zn element have better synergistic effect on improving the yield of the meta-anhydride.
[ example 10 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fractions of ferric nitrate, 0.1 mole fraction of lanthanum nitrate, 0.1 mole fraction of cerium nitrate and 0.2 mole fraction of zinc nitrate into the solution, and continuing the reaction at 60 ℃ for 1 hour. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 67.4%, the evaluation is shown in Table 1.
Compared with example 9, the lanthanide metals La and Ce and other active components of the present invention have a good synergistic effect in increasing the yield of the anhydride.
[ example 11 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fraction nickel nitrate, 0.2 mole fraction lanthanum nitrate, 0.1 mole fraction zinc nitrate and 0.1 mole fraction cadmium nitrate into the solution, and continuing to react for 1h at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 ═ water vapor0.05, and the mole yield of the metaanhydride is 67.6% when evaluated in a fixed bed reactor, and the evaluation results are detailed in Table 1.
Compared with example 9, the example shows that the group IIB elements Zn and Cd and other active components of the invention have better synergistic effect on improving the yield of the meta-anhydride.
[ example 12 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fractions of ferric nitrate, 0.2 mole fraction of lanthanum nitrate, 0.1 mole fraction of zinc nitrate and 0.1 mole fraction of cadmium nitrate into the solution, and continuing the reaction at 60 ℃ for 1 hour. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 67.5%, the evaluation is shown in Table 1.
[ example 13 ]
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 3 mole fractions of ferric nitrate, 0.1 mole fraction of lanthanum nitrate, 0.1 mole fraction of cerium nitrate, 0.1 mole fraction of zinc nitrate and 0.1 mole fraction of cadmium nitrate into the solution, and continuing to react for 1 hour at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c in a muffle furnace, and naturally cooling to obtain the catalyst. The catalyst is at the reaction temperature of 400 ℃ and the space velocity3000h-1the following, pseudocumene: steam 0.05, and the molar yield of the meta-anhydride was 68.2% when evaluated in a fixed bed reactor, the evaluation results are detailed in table 1.
Compared with the examples 10 and 11, V, Ti, Fe element of iron series metal, La and Ce element of lanthanide series metal, and Zn and Cd element of IIB group have very good synergistic effect on improving the yield of the partial anhydride.
Comparative example 2
61g of oxalic acid and 196ml of distilled water are weighed in a flask, stirred and heated to 84 ℃, 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 part of manganese nitrate and 0.2 mole part of cobalt nitrate into the solution, and continuing to react for 1 hour at 60 ℃. Adding 8 molar parts of titanium dioxide into 35ml 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 572 deg.c 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 62.8%, and the evaluation results are detailed in table 1.
TABLE 1
Claims (10)
1. the catalyst for synthesizing trimellitic anhydride 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, iron metal and at least one of lanthanide metal and IIB group element; the carrier of the catalyst is inert silicon carbide, alpha-alumina or ceramic ring.
2. The catalyst according to claim 1, wherein the iron-based element is at least one selected from the group consisting of Fe, Co and Ni.
3. The catalyst of claim 1, wherein the lanthanide is selected from at least one of La, Ce, Pr, Nd, Sm, and Eu.
4. The catalyst of claim 1 wherein the group IIB element is selected from at least one of Zn, Cd, and Hg.
5. The catalyst according to claim 1, wherein the molar ratio of the vanadium element, the titanium element and the iron-based metal element in the catalyst is 1: (1-15): (0.1-5).
6. the catalyst of claim 1 wherein the molar ratio of vanadium to the sum of the lanthanide metal and the group IIB element in the catalyst is from 1: (0.01-1).
7. A preparation method of the catalyst for synthesizing trimellitic anhydride by using any one of the catalysts described in claims 1-6, the preparation method is characterized by 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 iron series metal elements, lanthanide series metal elements and IIB 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.
8. The method according to claim 7, wherein the catalyst precursor is fed into a spray coater, heated at 124-353 ℃ and uniformly sprayed on the carrier.
9. the method according to claim 7, wherein the carrier coated with the catalyst precursor is calcined in a muffle furnace at 413-612 ℃ for 2-12 h.
10. A method for synthesizing trimellitic anhydride by using any one of the catalysts in claims 1-9, and is characterized in that trimellitic anhydride is synthesized by using trimellitic benzene, water vapor and air as raw materials and adopting a fixed bed reactor, wherein the feeding volume ratio of the trimellitic benzene 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)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566776.8A CN110560115B (en) | 2018-06-05 | 2018-06-05 | Catalyst for synthesizing trimellitic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566776.8A CN110560115B (en) | 2018-06-05 | 2018-06-05 | Catalyst for synthesizing trimellitic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110560115A true CN110560115A (en) | 2019-12-13 |
| CN110560115B CN110560115B (en) | 2021-11-30 |
Family
ID=68771949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810566776.8A Active CN110560115B (en) | 2018-06-05 | 2018-06-05 | Catalyst for synthesizing trimellitic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110560115B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10974225B1 (en) * | 2020-01-17 | 2021-04-13 | Zhejiang Nhu Company Ltd. | Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral |
| CN116262230A (en) * | 2021-12-13 | 2023-06-16 | 鞍山七彩化学股份有限公司 | Preparation method of 1, 8-naphthalene anhydride |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439636A (en) * | 2003-03-21 | 2003-09-03 | 黑龙江省石油化学研究院 | Production of metaphenyltrimethyl anhydride from metatrimethylbenzene by solid bed gas phase oxidation |
| WO2004011411A1 (en) * | 2002-07-30 | 2004-02-05 | Sk Chemicals Co., Ltd. | Method of producing trimellitic acid |
| CN1485304A (en) * | 2002-09-28 | 2004-03-31 | 宁波市贝特化工新材料有限公司 | One-step production of high-purity trimellitic acid from pseudocumene |
| CN1594302A (en) * | 2004-07-15 | 2005-03-16 | 中国石油化工股份有限公司 | Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process |
| US7378544B2 (en) * | 2003-12-18 | 2008-05-27 | Bp Corporation North America Inc. | Anthracene and other polycyclic aromatics as activators in the oxidation of aromatic hydrocarbons |
| CN101422727A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Benzoic anhydride catalyst and preparation method thereof |
| CN105339337A (en) * | 2013-06-26 | 2016-02-17 | 巴斯夫欧洲公司 | Process for preparing phthalic anhydride |
| CN105498817A (en) * | 2015-12-31 | 2016-04-20 | 江苏正丹化学工业股份有限公司 | Catalyst for production of trimellitic anhydride and preparation method and application of catalyst |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN107866241A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is made for durol oxidation |
-
2018
- 2018-06-05 CN CN201810566776.8A patent/CN110560115B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011411A1 (en) * | 2002-07-30 | 2004-02-05 | Sk Chemicals Co., Ltd. | Method of producing trimellitic acid |
| CN1485304A (en) * | 2002-09-28 | 2004-03-31 | 宁波市贝特化工新材料有限公司 | One-step production of high-purity trimellitic acid from pseudocumene |
| CN1439636A (en) * | 2003-03-21 | 2003-09-03 | 黑龙江省石油化学研究院 | Production of metaphenyltrimethyl anhydride from metatrimethylbenzene by solid bed gas phase oxidation |
| US7378544B2 (en) * | 2003-12-18 | 2008-05-27 | Bp Corporation North America Inc. | Anthracene and other polycyclic aromatics as activators in the oxidation of aromatic hydrocarbons |
| CN1594302A (en) * | 2004-07-15 | 2005-03-16 | 中国石油化工股份有限公司 | Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process |
| CN101422727A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Benzoic anhydride catalyst and preparation method thereof |
| CN105339337A (en) * | 2013-06-26 | 2016-02-17 | 巴斯夫欧洲公司 | Process for preparing phthalic anhydride |
| CN105498817A (en) * | 2015-12-31 | 2016-04-20 | 江苏正丹化学工业股份有限公司 | Catalyst for production of trimellitic anhydride and preparation method and application of catalyst |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN107866241A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is made for durol oxidation |
Non-Patent Citations (2)
| Title |
|---|
| OLGA V. ZALOMAEVA ET AL.: "Selective oxidation of pseudocumene and 2-methylnaphthalene with aqueous hydrogen peroxide catalyzed by g-Keggin divanadium-substituted polyoxotungstate", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| 高欣钦等: "用V-Ti-P-O系表面涂层催化剂气相催化氧化偏三甲苯制偏苯三酸酐", 《精细石油化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10974225B1 (en) * | 2020-01-17 | 2021-04-13 | Zhejiang Nhu Company Ltd. | Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral |
| CN116262230A (en) * | 2021-12-13 | 2023-06-16 | 鞍山七彩化学股份有限公司 | Preparation method of 1, 8-naphthalene anhydride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110560115B (en) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101772247B1 (en) | Improved mixed metal oxide ammoxidation catalysts | |
| KR20130007627A (en) | High efficiency ammoxidation process and mixed metal oxide catalysts | |
| CN110560115B (en) | Catalyst for synthesizing trimellitic anhydride | |
| WO2001028984A1 (en) | Method for producing acrylonitrile, catalyst for use therein and the method for preparing the same | |
| EP0032012B1 (en) | Oxidation and ammoxidation catalysts and their use | |
| CN107866257B (en) | Catalyst for preparing pyromellitic anhydride from durene | |
| CN117299142A (en) | Ammonia oxidation catalyst with selective co-product HCN production | |
| CN109647470B (en) | Catalyst for preparing partial anhydride | |
| WO2009022780A1 (en) | Method of preparing improved catalyst for production of acrylic acid | |
| CN110560111B (en) | Catalyst for synthesizing meta-anhydride from pseudocumene | |
| CN110560109B (en) | Catalyst for producing trimellitic anhydride | |
| CN110560110B (en) | Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene | |
| CN110560114B (en) | Catalyst for improving yield of trimellitic anhydride | |
| CN109647471B (en) | Catalyst for increasing yield of partial anhydride | |
| CN109647469B (en) | Catalyst for preparing partial anhydride | |
| CN109647466B (en) | Catalyst for synthesis reaction of partial anhydride | |
| CN110560116B (en) | Catalyst for oxidation of pseudocumene to prepare meta-anhydride | |
| CN110560112B (en) | Catalyst for preparing trimellitic anhydride | |
| CN109647465B (en) | Catalyst for synthesizing partial anhydride | |
| CN109647463B (en) | Catalyst for oxidation reaction of unsym-trimethyl benzene | |
| CN109647468B (en) | Catalyst for preparing meta-anhydride from pseudocumene | |
| CN110560113B (en) | Catalyst for pseudocumene catalytic oxidation | |
| CN114471645B (en) | Catalyst for producing isophthalonitrile by gas phase ammoxidation and preparation method and application thereof | |
| CN109647467B (en) | Catalyst for oxidation of pseudocumene | |
| JPH0517392A (en) | Production of acrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |