CN112473649B - Vanadium-based catalyst and preparation method and application thereof - Google Patents
Vanadium-based catalyst and preparation method and application thereof Download PDFInfo
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/06—Peri-condensed systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a vanadium-based catalyst, a preparation method and application thereof, wherein the vanadium-based catalyst comprises a vanadium-containing compound and a cocatalyst, and the cocatalyst is selected from one or more of a potassium-containing compound, a sodium-containing compound, a tin-containing compound and a germanium-containing compound. The vanadium-based catalyst can be used for synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride. The vanadium-based catalyst provided by the invention has high catalytic activity and good selectivity to 1,4,5, 8-naphthalene tetracarboxylic anhydride, and the synthetic method for synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride by using the vanadium-based catalyst is simple to operate, can be used for continuous production, and reduces the manufacturing cost of 1,4,5, 8-naphthalene tetracarboxylic anhydride.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a vanadium-based catalyst, a preparation method and application thereof, and particularly relates to application of the vanadium-based catalyst in synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride.
Background
1,4,5, 8-naphthalene tetracarboxylic anhydride is used for synthesizing monomers of high-temperature resistant high-molecular materials, and is used as an intermediate of dyes and pigments. The existing preparation method of 1,4,5, 8-naphthalene tetracarboxylic acid which is a raw material for producing 1,4,5, 8-naphthalene tetracarboxylic acid mainly comprises the following steps:
the pyrene route synthesis method can be used for directly oxidizing pyrene with dichromate in sulfuric acid to obtain naphthalene tetracarboxylic acid, or can be used for oxidizing pyrene with dichromate in sulfuric acid to obtain pyrene quinone, and then oxidizing pyrene quinone with sodium hypochlorite and potassium permanganate in alkaline medium to obtain 1,4,5, 8-naphthalene tetracarboxylic acid. The pyrene route has the following disadvantages: the pyrene is expensive, the yield of naphthalene tetracarboxylic acid is only 52%, and a large amount of waste liquid is generated.
The method for preparing 1,4,5, 8-naphthalene tetracarboxylic acid from the malononitrile has more reaction steps, higher malononitrile cost and higher technical requirements.
The yield of 1,4,5, 8-naphthalene tetracarboxylic acid was 69% by the diketene method. The method consumes anhydrous aluminum chloride, has waste liquid, and has large consumption of diketene and anhydrous hydrogen fluoride and high production cost.
Based on the above problems, a new synthesis method of 1,4,5, 8-naphthalene tetracarboxylic anhydride needs to be continuously explored, so as to meet the requirements of industry on high-quality and low-price 1,4,5, 8-naphthalene tetracarboxylic anhydride, and the requirements of simplifying process conditions and continuous production.
Disclosure of Invention
In order to overcome the problems, the inventor has conducted intensive researches and designs a vanadium-based catalyst, a preparation method and application thereof, wherein the catalyst uses a vanadium-containing compound as a main catalyst, a potassium-containing compound and a tin-containing compound as a cocatalyst which are supported on pumice, the preparation method is simple, the catalyst activity is high, and crude pyrene and an oxidant react under the action of the vanadium-based catalyst to generate 1,4,5, 8-naphthalene tetracarboxylic anhydride, so that the invention is completed.
In particular, it is an object of the present invention to provide the following aspects:
the first aspect of the invention provides a vanadium-based catalyst comprising a main catalyst and a cocatalyst, the main catalyst being a vanadium-containing compound, and the cocatalyst being selected from one or more of potassium, sodium, magnesium, calcium, tin, germanium and lead-containing compounds.
In a second aspect the present invention provides a process for the preparation of a vanadium-based catalyst, preferably for the preparation of a vanadium-based catalyst according to the first aspect of the invention, the process comprising the steps of:
step 1, dissolving a vanadium-containing compound, a potassium-containing compound and a tin-containing compound in a solution to obtain a mixed solution I;
step 2, adding acid into the mixed solution I for reaction to obtain a mixed solution II;
and 4, roasting the concentrated solution to obtain the vanadium-based catalyst.
The third aspect of the invention provides the use of the vanadium-based catalyst according to the first aspect of the invention in a method for synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride, wherein the method comprises the step of reacting pyrene with an oxidant under the action of the vanadium-based catalyst to generate 1,4,5, 8-naphthalene tetracarboxylic anhydride.
Drawings
FIG. 1 shows a gas chromatogram of 1,4,5, 8-naphthalene tetracarboxylic anhydride;
FIG. 2 shows a gas chromatogram of a 1,4,5, 8-naphthalene tetracarboxylic anhydride standard.
Detailed Description
The invention is further described in detail below by means of the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The invention provides a vanadium-based catalyst, which comprises a main catalyst and a cocatalyst, wherein the main catalyst is a vanadium-containing compound, and the cocatalyst is one or more selected from potassium-containing, sodium-containing, magnesium-containing, calcium-containing, tin-containing, germanium-containing and lead-containing compounds.
According to a preferred embodiment of the invention, the vanadium containing compound is one or more of ammonium metavanadate, vanadium trichloride, vanadate and vanadium pentoxide, preferably ammonium metavanadate.
According to a preferred embodiment of the present invention, the promoter is one or more of a potassium-containing compound, a sodium-containing compound, a tin-containing compound and a germanium-containing compound, preferably a potassium-containing compound and a tin-containing compound.
The inventors have found through a large number of experiments that when the cocatalyst is a potassium-containing compound and a tin-containing compound, the raw material pyrene can be oxidized to an acid, which is then dehydrated at a high temperature to produce an anhydride. The catalyst prepared from the potassium-containing compound and the tin-containing compound has the highest catalytic activity, and the selectivity of 1,4,5, 8-naphthalene tetracarboxylic anhydride can reach more than 80 percent.
According to a preferred embodiment of the present invention, the potassium-containing compound is selected from one or more of potassium nitrate, potassium sulfate, potassium chloride, preferably potassium sulfate.
According to a preferred embodiment of the present invention, the tin-containing compound is selected from one or more of stannous chloride, stannic methane sulfonate and stannic ethane sulfonate, preferably stannous chloride.
According to a preferred embodiment of the invention, the composition of the catalyst is V a Sn b K c O x Wherein a=1, b=0.5-1.0, c=0.1-0.5, and x=3.
Wherein a, b and c in the composition of the catalyst in the present invention correspond to the amounts of the respective elements in the raw materials added when preparing the catalyst, respectively.
In a further preferred embodiment a=1, b=0.65-0.90, c=0.11-0.35, x=3.
In a still further preferred embodiment, a=1, b=0.86, c=0.19, x=3.
According to a preferred embodiment of the invention, the catalyst further comprises a support selected from one or more of kaolinite, porcelain rings, activated carbon or pumice, preferably pumice.
Pumice stone is also called light stone or pumice stone, is a vitreous acidic volcanic eruption rock with more pores, light weight and small volume weight, has the advantages of high strength, acid and alkali resistance and corrosion resistance, and is pollution-free and radioactive-free, and is an ideal catalyst carrier.
According to a preferred embodiment of the invention, the pumice stone has a particle size of 2-10mm, preferably 3-8mm, more preferably 4-6mm.
According to a preferred embodiment of the invention, the pumice stone has a water absorption of 50-60%, preferably 54-56%; the porosity of the pumice stone is 70-80%, preferably 74-76%.
According to a preferred embodiment of the invention, the mass of the support represents 70-90% of the total mass of the vanadium-based catalyst.
Wherein, the total mass of the vanadium-based catalyst refers to the sum of the mass of the main catalyst, the cocatalyst and the carrier.
In a further embodiment, the mass of the support is 75-85% of the total mass of the vanadium-based catalyst.
In a further embodiment, the mass of the support is 76-78% of the total mass of the vanadium-based catalyst.
The second aspect of the present invention provides a method for preparing a vanadium-based catalyst, the method comprising the steps of:
step 1, dissolving a vanadium-containing compound, a potassium-containing compound and a tin-containing compound in a solution to obtain a mixed solution I;
according to a preferred embodiment of the invention, the solution is one or more of oxalic acid solution, carbonic acid solution, formic acid solution and acetic acid solution, preferably oxalic acid solution.
The purpose of the acid solution is to improve the solubility of the vanadium-containing compound, so that the prepared catalyst element is distributed more uniformly.
According to a preferred embodiment of the present invention, the oxalic acid solution has a mass concentration of 4 to 15%, more preferably 8 to 12%, still more preferably 10%.
According to a preferred embodiment of the invention, in step 1, the molar ratio of vanadium-containing compound to tin-containing compound and potassium-containing compound is 1: (0.5-1.0): (0.1-0.5).
Wherein the molar ratio of the vanadium-containing compound to the tin-containing compound and the potassium-containing compound refers to the molar ratio of the vanadium element, the tin element and the potassium element.
In a further preferred embodiment, the molar ratio of vanadium-containing compound to tin-containing compound and potassium-containing compound is 1: (0.65-0.90): (0.11-0.35).
In a still further preferred embodiment, the molar ratio of vanadium-containing compound to tin-containing compound and potassium-containing compound is 1:0.86:0.19.
the inventors found that the molar ratio of the vanadium-containing compound to the tin-containing compound and the potassium-containing compound was 1: (0.5-1.0): (0.1 to 0.5), for example, the molar ratio of the vanadium-containing compound to the tin-containing compound and the potassium-containing compound is 1:0.86: at 0.19, the catalyst obtained has the best catalytic performance, and the selectivity of 1,4,5, 8-naphthalene tetracarboxylic anhydride can reach more than 80 percent.
According to a preferred embodiment of the invention, in step 1, the mixture I is heated to 50-120 ℃, more preferably to 70-90 ℃, still more preferably to 80 ℃.
Wherein the purpose of heating is to accelerate the dissolution rate of the vanadium-containing compound with the potassium-containing compound and the tin-containing compound in the solution.
Step 2, adding acid into the mixed solution I for reaction to obtain a mixed solution II;
according to a preferred embodiment of the present invention, in step 2, the acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, and more preferably hydrochloric acid.
According to a preferred embodiment of the present invention, the mass concentration of the hydrochloric acid is 30 to 36%, more preferably 32 to 35%, still more preferably 33%.
Wherein the purpose of the acid addition is to promote the uniform adsorption of the subsequent active components inside the carrier, thereby introducing strongly adsorbed ions into the prepared catalyst.
According to a preferred embodiment of the invention, in step 2, the stirring is carried out after the addition of the acid for a period of time ranging from 10 to 60 minutes, preferably from 20 to 40 minutes, more preferably 30 minutes.
according to a preferred embodiment of the invention, the support is selected from one or more of kaolinite, porcelain rings, activated carbon or pumice, preferably pumice.
According to a preferred embodiment of the invention, the pumice stone has a particle size of 2-10mm, preferably 3-8mm, more preferably 4-6mm.
According to a preferred embodiment of the invention, the pumice stone has a water absorption of 50-60%, preferably 54-56%; the porosity of the pumice stone is 70-80%, preferably 74-76%.
According to a preferred embodiment of the invention, the pumice stone is subjected to an acid wash treatment before addition.
Wherein, the acid washing can remove a small amount of metal impurities in the pumice.
According to a preferred embodiment of the invention, the mass of the support represents 70-90% of the total mass of the vanadium-based catalyst.
Wherein, the total mass of the vanadium-based catalyst refers to the sum of the mass of the main catalyst, the cocatalyst and the carrier.
In a further embodiment, the mass of the support is 75-85% of the total mass of the vanadium-based catalyst. In a further embodiment, the mass of the support is 76-78% of the total mass of the vanadium-based catalyst
According to a preferred embodiment of the present invention, the concentration is carried out at 80-120 ℃, further preferably 90-110 ℃, more preferably 105 ℃.
According to a preferred embodiment of the invention, the mixture II is concentrated to a form.
Wherein, the concentration to the forming refers to heating the mixed liquid until the liquid is basically not remained.
And 4, roasting the concentrated solution to obtain the vanadium-based catalyst.
According to a preferred embodiment of the invention, the calcination is carried out at 200-450 ℃ for 1-5 hours, then heated to 400-900 ℃ for 2-10 hours.
In a further preferred embodiment, the calcination is carried out at 250-400℃for 1-3 hours, followed by a temperature increase to 500-700℃for a further 8-10 hours.
In a still further preferred embodiment, the calcination is carried out at 300℃for 2 hours, followed by a temperature increase to 650℃for a further 6 hours.
The main purpose of roasting at low temperature is to clean out excessive oxalic acid in the catalyst, and then to perform high-temperature roasting mainly in the heat treatment process of the catalyst, namely the activation process of the catalyst and the grain distribution or growth process, wherein different roasting temperatures and time periods can influence the activity of the catalyst, and the catalyst has the defects of over-low temperature, incomplete roasting and incomplete structure. And if the temperature is too high, the catalyst is sintered into blocks, so that the active sites are seriously reduced, and the activity of the catalyst is reduced.
According to a preferred embodiment of the invention, after roasting, naturally cooling to obtain the vanadium-based catalyst, wherein the particle size of the vanadium-based catalyst is 4-6mm.
The third aspect of the invention provides the use of the vanadium-based catalyst of the first aspect of the invention in a method for synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride, wherein the method comprises the step of reacting pyrene with an oxidant under the action of the vanadium-based catalyst to generate 1,4,5, 8-naphthalene tetracarboxylic anhydride.
According to a preferred embodiment of the invention, the oxidizing agent is a solid oxidizing agent, a liquid oxidizing agent or a gaseous oxidizing agent, preferably a gaseous oxidizing agent.
According to a preferred embodiment of the invention, the gaseous oxidizing agent is ozone or oxygen, preferably oxygen.
Ozone has strong oxidizing property, but the strong oxidizing property of ozone is harmful to human health. Therefore, in the present invention, oxygen is preferable as the gas oxidizing agent.
In a preferred embodiment, the oxygen is diluted with a chemically inert gas.
Wherein, the gas with chemical inertness refers to a gas which does not undergo chemical reaction under the reaction conditions described in the invention. In the invention, pure oxygen is adopted to easily cause severe chemical reaction, so that the reaction condition is difficult to control, and potential safety hazard is easily caused, thus the oxygen needs to be diluted.
In a preferred embodiment, the chemically inert gas is selected from helium, argon, neon or nitrogen, preferably nitrogen.
Since the main components of air are oxygen and nitrogen, in the present invention, air is preferably selected as the oxidizing agent for producing 1,4,5, 8-naphthalene tetracarboxylic anhydride. Through the reaction of pyrene and oxygen in the air, 1,4,5, 8-naphthalene tetracarboxylic anhydride is produced.
According to the present invention, the equation for the reaction of pyrene and oxygen in air under the action of a vanadium-based catalyst is shown as the following formula (1):
side reactions, such as reaction of pyrene with oxygen in air to water and carbon dioxide, are also associated with the synthesis of 1,4,5, 8-naphthalene tetracarboxylic anhydride.
According to a preferred embodiment of the invention, the synthesis is carried out in a fluidized bed reactor.
The fluidized bed is used as a reactor, so that the continuous production of 1,4,5, 8-naphthalene tetracarboxylic anhydride can be realized, and the production efficiency is improved.
According to a preferred embodiment of the invention, the pyrene is crude pyrene, the content of pyrene in the crude pyrene is more than or equal to 95%, and generally, the impurities in the crude pyrene are impurities in coal tar, so that the purity of a target product is not affected. This is mainly because impurities in crude pyrene are directly decomposed into carbon dioxide and water under high temperature conditions and do not enter the product.
According to a preferred embodiment of the invention, the pyrene is preheated to 200-380 ℃, preferably 240-340 ℃, more preferably 300-320 ℃.
At normal temperature and pressure, pyrene is an almost white crystal, and the purpose of preheating treatment is to convert the pyrene from a solid state to a liquid state, and the pyrene can be conveyed into a reactor through a metering pump.
According to a preferred embodiment of the invention, the molar ratio of pyrene to air is 1:70-95.
In a further preferred embodiment, the molar ratio of pyrene to air is 1:80-90.
In a still further preferred embodiment, the molar ratio of pyrene to air is 1:86.
Wherein the molar quantity of air is calculated in a standard condition, and 1mol is calculated per 22.4L of air in the standard condition, and the molar quantity of air can be calculated according to the volume of air. The air has mainly three functions, the first function is to provide oxygen for the reaction, the second function is to provide driving force for the carrier gas of the fluidized bed reactor, so that the catalyst is in a suspended state, and the third function is to bring the generated product out of the fluidized bed reactor. Therefore, the air is used in an amount much larger than that of pyrene.
According to a preferred embodiment of the present invention, the pyrene and air are introduced into the fluidized-bed reactor after being mixed, and the mixture of pyrene and air is heated to 200-380 ℃, preferably 240-360 ℃, more preferably 300-350 ℃ during the mixing.
According to a preferred embodiment of the present invention, the catalyst is a vanadium-based catalyst, the loading of the catalyst being from 0.10 to 0.25g/cm 3 Preferably 0.14-0.20g/cm 3 More preferably 0.176g/cm 3 。
Wherein, in the present invention, the loading of the catalyst refers to the mass of the catalyst added per unit volume of the fluidized bed reactor. The inventor finds that too much catalyst loading can increase the density of the catalyst in the fluidized bed reactor, so that the collision among catalyst particles is increased, and the catalyst abrasion loss is easy to cause; the filling amount of the catalyst is too small, which is not beneficial to accelerating the reaction rate, and simultaneously reduces the processing capacity of the fluidized bed reactor, which is not beneficial to industrial production.
According to a preferred embodiment of the invention, the catalyst has a weight loading of 0.05 to 0.5/h, preferably 0.1 to 0.3/h, more preferably 0.2/h.
Wherein the weight loading of the catalyst refers to space velocity, which refers to the amount of feedstock passing through the unit catalyst per unit time, reflecting the residence time of the feedstock in the catalyst bed. The greater the space velocity, the shorter the residence time, the lower the reaction depth, but the greater the throughput. The smaller the space velocity, the longer the residence time, the greater the reaction depth, but the reduced throughput. The inventors have found through extensive studies that when the air velocity is within the above range, the throughput of the fluidized bed reactor is maximized and the output 1,4,5, 8-naphthalene tetracarboxylic acid anhydride product can reach 0.45mol/h.
According to a preferred embodiment of the present invention, the reaction is carried out at 300-550℃and 0.01-0.05 MPa.
In a further preferred embodiment, the reaction is carried out at 380-480℃and 0.01-0.02 MPa.
In a still further preferred embodiment, the reaction is carried out at 440℃and 0.01MPa.
According to a preferred embodiment of the invention, 1,4,5, 8-naphthalene tetracarboxylic anhydride is collected using a trap.
After the reaction was completed, the gas coming out of the fluidized bed reactor was mainly 1,4,5, 8-naphthalene tetracarboxylic anhydride, carbon dioxide and water, and no pyrene was detected, indicating that pyrene was completely reacted in the fluidized bed reactor. 1,4,5, 8-naphthalene tetracarboxylic anhydride is directly condensed on the inner wall of the catcher after meeting the catcher, and the catcher catches 1,4,5, 8-naphthalene tetracarboxylic anhydride, except a small amount of water, has no other impurities basically, and the purity of the product is as high as 99.5 percent.
According to a preferred embodiment of the invention, the reaction tail gas from the trap is absorbed by a tail gas absorbing device comprising an aqueous absorption tank through which the reaction tail gas is discharged to the atmosphere.
The invention has the beneficial effects that:
1) The preparation method of the 1,4,5, 8-naphthalene tetracarboxylic anhydride catalyst provided by the invention is simple and convenient to operate, mild in reaction condition and strong in operability;
2) The activity of the 1,4,5, 8-naphthalene tetracarboxylic anhydride catalyst provided by the invention is up to 80%, even up to 87%, and the selectivity of the catalyst is up to 80%, even up to 87%.
3) The synthesis method of the 1,4,5, 8-naphthalene tetracarboxylic anhydride adopted by the invention is carried out in a fluidized bed reactor, so that continuous production can be realized, and the production efficiency of the 1,4,5, 8-naphthalene tetracarboxylic anhydride is improved;
4) The synthesis method of 1,4,5, 8-naphthalene tetracarboxylic anhydride adopted by the invention takes pyrene and air as raw materials for reaction, the raw materials are easy to obtain, the synthesis route is short, the utilization rate of the raw materials is high, the side reaction in the reactor is less, and the amount of three wastes generated after the synthesis is finished is less, thus the synthesis method is a green synthesis method.
Examples
Example 1 preparation of catalyst
Respectively dissolving 10.5g of ammonium metavanadate, 17.5g of stannous chloride and 3g of potassium sulfate slowlySlowly dissolving in 212.5g of aqueous solution containing 23.4g of oxalic acid, adding 0.025g of industrial hydrochloric acid at 80 ℃, stirring for 0.5h, adding the solution into 0.25L (110 g) of pumice subjected to screening and acid washing, uniformly stirring, concentrating to form, taking out, placing in a muffle furnace, gradually heating to 300 ℃, pre-roasting for 2h, heating to 650 ℃, preserving heat for 6h, and cooling to room temperature to obtain the vanadium-based catalyst V 1 Sn 0.86 K 0.19 O 3 And bottling the obtained vanadium-based catalyst for standby.
Example 2 Synthesis of 1,4,5, 8-naphthalene tetracarboxylic anhydride
120g of the catalyst prepared in accordance with the method of example 1 was charged into a glass fluidized-bed reactor having a height of 600mm of phi 38mm, after which crude pyrene was preheated to 300℃and mixed with air, and during the mixing, the raw materials were heated to 350℃and then introduced into the glass fluidized-bed reactor. Wherein, the mol ratio of industrial acenaphthene to air=1:86, the purity of crude pyrene is 95.2 percent, the adding amount is 51g, the weight load of the catalyst is 0.2/h, the reaction temperature is 440+/-5 ℃, and the pressure of the reaction system is 0.01MPa.
After the end of the experiment, 51.7g of product was collected in the trap. Through detection, no pyrene remains in the product, and the pyrene conversion rate reaches 100%. The product contains 1,4,5, 8-naphthalene tetracarboxylic anhydride, the product contains 0.11% of water, and the yield of the 1,4,5, 8-naphthalene tetracarboxylic anhydride is up to 87%. The obtained 1,4,5, 8-naphthalene tetracarboxylic anhydride had an appearance of white-like crystals.
The obtained product was dried and dissolved in methylene chloride for gas chromatography characterization, and the result is shown in fig. 1. The gas chromatograph 2 of the standard 1,4,5, 8-naphthalene tetracarboxylic anhydride was compared with that of FIG. 1.
Wherein, the chromatographic peak appearing at 7.458min in fig. 2 is 1,4,5, 8-naphthalene tetracarboxylic anhydride, and the peak appearing at 7.276min in fig. 1 is 1,4,5, 8-naphthalene tetracarboxylic anhydride, the peak area is 1942812uv, and the peak area ratio is 99.7750% by comparison with fig. 2. Chromatographic peaks occurring at 1.727min, 3.060min and 5.217min are impurity peaks with peak areas of 1956uv, 1083uv and 1342uv respectively, and peak area ratios of 0.1004%, 0.0556% and 0.0689% respectively. The purity of 1,4,5, 8-naphthalene tetracarboxylic anhydride thus calculated was 99.78%.
The invention has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the invention can be subjected to various substitutions and improvements, and all fall within the protection scope of the invention.
Claims (3)
1. Use of a vanadium-based catalyst characterized in that: the vanadium-based catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is a vanadium-containing compound, and the cocatalyst is selected from a potassium-containing compound and a tin-containing compound;
the vanadium-based catalyst is prepared by a method comprising the following steps:
step 1, dissolving a vanadium-containing compound, a potassium-containing compound and a tin-containing compound in a solution to obtain a mixed solution I, wherein the vanadium-containing compound is ammonium metavanadate;
step 2, adding acid into the mixed solution I for reaction to obtain a mixed solution II;
step 3, adding a carrier into the mixed solution II, and concentrating to obtain a concentrated solution, wherein the carrier is pumice;
step 4, roasting the concentrated solution to obtain a vanadium-based catalyst, wherein the roasting is firstly carried out for 1-3 hours at 200-450 ℃, and then the temperature is raised to 650 ℃ and then carried out for 6 hours;
in step 1, the molar ratio of the vanadium-containing compound to the tin-containing compound to the potassium-containing compound is 1: (0.65-0.90): (0.11-0.35);
the vanadium-based catalyst is used for catalyzing and synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride, in the method for synthesizing 1,4,5, 8-naphthalene tetracarboxylic anhydride, pyrene and an oxidant react in the presence of the vanadium-based catalyst to generate 1,4,5, 8-naphthalene tetracarboxylic anhydride,
the reaction is carried out in a fluidized bed reactor,
air is used as an oxidant for preparing 1,4,5, 8-naphthalene tetracarboxylic anhydride,
the molar ratio of the pyrene to the air is 1:70-95, and the reaction is carried out at 380-480 ℃ and 0.01-0.02 MPa.
2. Use according to claim 1, characterized in that: in step 2, the acid is selected from one or more of sulfuric acid, hydrochloric acid or nitric acid.
3. Use according to claim 2, characterized in that: the acid is hydrochloric acid.
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