A method for preparing a FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor

Abstract

The application discloses a preparation method of a FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor in the technical field of catalyst devices, which adopts a sol-gel method to prepare FeCeO3 sol, then adopts a chemical deposition method to prepare FeVO4-FeCeO3 nanoparticles, finally, the FeVO4-FeCeO3 nanoparticles, red mud clay and activated carbon are ground, sieved and uniformly mixed, PVA, aluminum oxide, magnesium oxide, graphite powder and PMA are added, and then the mixture is molded and calcined to obtain the porous ceramic membrane catalytic reactor. The porous ceramic membrane catalytic reactor can be used for synthesizing special resin monomers, can improve the catalyst activity and product yield, can reduce energy consumption, can meet the need of further expanding the production capacity, and can make the production cost of the special resin monomers low and the production efficiency high.

Description

TECHNICAL FIELD

[0001] The application relates to a dehydrogenation catalyst device, in particular to a preparation method of a dehydrogenation catalytic reactor for synthesizing special resin monomers, and belongs to the technical field of chemical industry. BACKGROUND

[0002] The special resin monomer contains vinyl / isopropenyl monomers, mainly vinyl monomers and isopropenyl monomers, including vinyltoluene, divinylbenzene, p-methylstyrene, p-tert-butylstyrene, alpha-methylstyrene, m-diisopropenylbenzene and p-diisopropenylbenzene. Vinyl / isopropenyl special resin monomers are widely used in new energy wind power, high-speed rail and new energy automobile motor, biological medicine, environmental protection, food hygiene and energy-saving building industries, and the huge demand provides strong guarantee for the development of the special resin monomer industry.

[0003] At present, the dehydrogenation synthesis of ethylbenzene / isopropylbenzene derivatives into vinyl / isopropenyl monomers is mainly synthesized by a catalytic dehydrogenation method. The conventional dehydrogenation catalyst is a Fe-based catalyst, which uses alkali metals and alkaline earth metals to control the surface acidity and catalytic activity of the catalyst. Considering the environmental factors, scientists use Ce-containing metal oxides to replace traditional Cr-containing metal oxides, and add a small amount of noble metals and rare earth metals to solve the problems of easy carbon deposition and high water / oil ratio in industrial synthesis. Specifically, by adding noble metal oxides and rare earth oxides to the Fe-K-Ce system, a stable lattice structure is formed through coordination, thereby improving the stability and activity of the catalyst. However, the catalyst has complex components, high manufacturing difficulty and high cost.

[0004] At present, the following related technical solutions are disclosed in the patent database:

[0005] CN109665929A discloses a catalyst for producing vinyltoluene, a preparation method and application thereof. The catalyst is prepared by using a porous ceramic membrane prepared from pollutionary red mud waste slag discharged during the extraction of aluminum oxide in the aluminum industry, aluminum source powder, activated carbon powder and a forming agent solution as a carrier, and using iron-copper-niobium composite oxides as a catalytically active component. The red mud waste slag, aluminum source powder, activated carbon powder and forming agent solution are crushed, dosed, granulated, formed and calcined to prepare the porous ceramic membrane carrier. The porous ceramic membrane carrier is immersed in an active component precursor composite solution, and then dried and calcined to obtain the catalyst for producing vinyltoluene. When the catalyst is applied to the dehydrogenation of methylbenzene to produce vinyltoluene, it has the advantages of high raw material conversion rate, good product selectivity, low energy consumption and inhibition of surface carbon deposition, and has a broad market application prospect.

[0006] CN107790149A relates to a catalyst for dehydrogenation of diethylbenzene and a preparation method thereof, mainly solving the problem of low catalyst activity and high ratio of mono-olefin to di-olefin in the product in the prior art. The catalyst for dehydrogenation of diethylbenzene comprises the following components in percentage by weight: 65-80% of FeO; 6-14% of KO; 8-14% of CeO; 0.5-5% of MoO; 0.5-5% of CaO; 0.5-2% of NaO; and at least one or several selected from MnO, TiO or PrO, with a content of 0.1-3.5%. The technical solution preferably solves the above technical problems, effectively improves the activity of the catalyst and reduces the ratio of mono-olefin to di-olefin in the product during the preparation of divinylbenzene by dehydrogenation of diethylbenzene, and can be used in the industrial production of divinylbenzene by dehydrogenation of diethylbenzene.

[0007] CN105562023A relates to a catalyst for preparing p-methylstyrene and a preparation method thereof, mainly solving the problem of low catalyst activity in the prior art. The catalyst for preparing p-methylstyrene comprises the following components in percentage by weight: 65-81% of Fe2O3; 8-14% of K2O; 6-13% of CeO2; 0.3-5% of Mo2O3 or / and WO3; and at least one of 0.3-7% of alkaline earth metal oxides. The technical solution preferably solves the problem of catalyst activity and can be used in the industrial production of p-methylstyrene by dehydrogenation of p-methylstyrene.

[0008] CN101829576A discloses a catalyst for dehydrogenation of ethylbenzene and a preparation method thereof. The catalyst is prepared by adding various metal oxides stabilizing aids WO3 and / or MoO3, CaO, BaO, CuO, ZnO2, Co2O3, La2O3 to a catalyst with Fe-K-Ce-Mo (or W or Mo-W) as the main system. The catalyst has high activity and selectivity, low deactivation rate and high stability, and is suitable for dehydrogenation of ethylbenzene to styrene, dehydrogenation of isopropylbenzene to isopropylbenzene, and dehydrogenation of p-methylisopropylbenzene to p-methylisopropylbenzene. The catalyst is prepared by a kneading method.

[0009] Existing catalysts for dehydrogenation mainly include Fe-K system and Fe-K-Ce system. The Fe-K system catalyst cannot adapt to low water-oil ratio operating environment, has low catalytic activity and is difficult to regenerate in lattice structure. The Fe-K-Ce system catalyst has complex composition, is difficult to manufacture and has high cost. The existing dehydrogenation catalysts are difficult to meet the requirements of continuous normal pressure or slightly positive pressure high-temperature high-efficiency dehydrogenation in industry. SUMMARY

[0010] In order to overcome the defects of the prior art, the application provides a preparation method of a FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor, which can be used as a dehydrogenation catalyst for synthesizing special resin monomers, can improve catalyst activity and product yield, reduces energy consumption, meets the need of further expanding production capacity, and makes the production cost of the special resin monomers low and the production efficiency high.

[0011] To this end, the technical scheme of the application is as follows:

[0012] The application provides a preparation method of a FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor, which comprises the following steps:

[0013] (1) preparing FeCeO3 sol by a sol-gel method

[0014] Ce(NO3)4, Fe(NO3)3 and sodium citrate are dissolved in distilled water, then liquid polyethylene glycol (PEG200-1000) is added; the mixed solution is fully stirred and reacted in a microwave chemical device to obtain FeCeO3 sol; the PEG is a pore former for the FeCeO3 sol; the sodium citrate is used for adjusting the pH value of the reaction solution; the mass ratio of the amounts of Ce(NO3)4, Fe(NO3)3 and sodium citrate is 1.1: (0.9-1.1): (1.1-1.3); the reaction temperature is 60-90 DEG C; and the reaction time is 1-10 h;

[0015] (2) preparing FeVO4-FeCeO3 nanoparticles by a chemical deposition method

[0016] V2O5 is dispersed in deionized water, then the V2O5 suspension and the FeCeO3 sol prepared in step (1) are fully stirred, and after being uniformly mixed, are placed in a microwave chemical device to react under certain temperature and pressure; after being subjected to acid washing, water washing, drying and calcination annealing, FeVO4-FeCeO3 nanoparticles are obtained; the mass ratio of the amounts of V2O5 and FeCeO3 used is (0.25-0.5): 1; the temperature of the microwave chemical device is 140-160 DEG C, and the pressure is 3.5-4.5 MPa;

[0017] (3) preparing a ceramic membrane catalytic reactor

[0018] FeVO4-FeCeO3 nanoparticles, red mud clay and activated carbon prepared in step (2) are ground and sieved in a certain ratio, then are uniformly mixed, polyvinyl alcohol (PVA), aluminum oxide, magnesium oxide, graphite powder and propylene glycol methyl ether acetate (PMA) are added, then the mixture is added into a mold to be press-formed to obtain a ceramic membrane ligand, and the ceramic membrane ligand after pressure keeping is placed in a muffle furnace to be calcined at high temperature, so that a porous ceramic membrane catalytic reactor is obtained.

[0019] The PEG in step (1) is 0.5-0.85 times the mass of Ce(NO3)4, and the distilled water is 20-30 times the mass of Ce(NO3)4.

[0020] Further, the temperature of the microwave chemical device in step (1) is 75℃, and the time of the microwave chemical device is 2h.

[0021] Further, the deionized water dispersion time in step (2) is 1h, the reaction time is 30min, and the stirring time is 30min.

[0022] Further, the temperature of the microwave chemical device in step (2) is 150℃, and the pressure of the microwave chemical device is 4.0MPa.

[0023] Further, the calcination annealing temperature in step (2) is 650-700℃.

[0024] Further, the mass ratio of FeVO4-FeCeO3 nanoparticles, red mud clay, activated carbon, PVA, aluminum oxide, magnesium oxide, graphite powder and PMA in step (3) is (1-2):30:10:1:(1-2):(55-60):(1.5-2):(0.5-1).

[0025] Further, the calcination temperature of the muffle furnace in step (3) is 600℃, and the time is 2h.

[0026] The sodium citrate in the technical solution functions to adjust the surface pH value of the catalyst, the PEG functions as a sol pore-forming agent, FeVO4-FeCeO3 is the catalytically active center, PVA is a forming agent for the ceramic membrane catalytic reactor, aluminum oxide is a binder for the ceramic membrane catalytic reactor, graphite powder and PMA are pore-forming agents for the ceramic membrane catalytic reactor, and magnesium oxide is a sintering aid for the ceramic membrane catalytic reactor.

[0027] Compared with the prior art, the present application has the following advantages:

[0028] (1) The dehydrogenation catalyst uses single-atom catalysis principle, uses the FeOx crystal lattice structure constructed by Ce and V as an active carrier, successfully prepares FeVO4-FeCeO3 nanoparticles, and coordinates and constructs the active components of the catalyst by introducing FeVO4-FeCeO3 nanoparticles, so that the crystal lattice structure of the catalyst is more stable and has better ductility;

[0029] (2) The super-hydrophilic catalyst carrier is used to make the carrier have larger flux and better thermal conductivity, which is conducive to reducing the mass transfer resistance in the reaction system and improving the entropy value of the reaction system, thereby reducing the reaction energy consumption;

[0030] (3) The synthesized catalyst can be used as a dehydrogenation catalyst for synthesizing special resin monomers, which can improve the catalyst activity and product yield, reduce energy consumption, and meet the needs of further expanding production capacity. The production cost of the synthesized special resin monomers is low, and the production efficiency is high. DETAILED DESCRIPTION

[0031] The application will be further described below in combination with specific implementation examples.

[0032] The catalytic performance analysis test includes the following two parts:

[0033] (i) Activity evaluation test

[0034] A catalyst of a certain size or weight is loaded in a fixed reaction bed, and the effect of the catalyst on the dehydrogenation of ethylbenzene / isopropylbenzene derivatives to synthesize vinyl / isopropyl monomers is investigated under different water / oil ratios (volume ratio), space velocities, pressures, reaction temperatures, and preheating temperatures. After the reaction is completed, the vinyl / isopropyl monomers after liquid separation are determined by gas chromatography (GC), and the raw material conversion rate (X%), target product selectivity (S%) and yield (Y%) are calculated according to the determination results: A S Y

[0035]

[0036]

[0037]

[0038] wherein C 0 (%) and C t (%) are the concentrations of ethylbenzene / isopropylbenzene derivatives before and after the reaction, C 1 (%) is the concentration of the generated vinyl / isopropyl monomers.

[0039] (ii) Stability evaluation test

[0040] During the activity evaluation test, the feed flow rate and temperature are recorded every 1 h, and the sample vinyl / isopropyl monomer content is analyzed every 2 h to investigate the service life of the catalyst. The vinyl toluene is mainly selected for stability evaluation for 30 days, and the activity reduction rate (R%) is calculated according to the test results: D

[0041]

[0042] A wherein​​​​0 (%) and A t (%) are the first vinyltoluene conversion rate after the reaction is stable and the raw material conversion rate after the reaction for 30 days, respectively. Example 1

[0043] (1) Preparation of FeCeO3 sol by sol-gel method

[0044] FeCeO3 sol was prepared by microwave chemical device assisted sol-gel method. The specific process is as follows: 4.0 g of Ce(NO3)4, 4.0 g of Fe(NO3)3 and 4.8 g of sodium citrate were dissolved in 100 mL of distilled water, then 3 mL of polyethylene glycol 200 (PEG200, density 1.125 g / mL, 3.375 g) was added, and the mixed solution was stirred at 75℃ in the microwave chemical device for 10 h to obtain FeCeO3 sol.

[0045] (2) Preparation of FeVO4-FeCeO3 nanoparticles by chemical deposition method

[0046] 0.5 g of V2O5 was ultrasonically dispersed in deionized water for 1 h, then the V2O5 suspension and 87 g of FeCeO3 sol prepared in step (1) (wherein the net content of FeCeO3 is 2 g) were fully stirred for 30 min, and then the mixture was placed in a microwave chemical device and reacted at 150℃ and 4.0 MPa for 30 min. Finally, after acid washing, water washing, drying and calcining annealing at 650~700℃, FeVO4-FeCeO3 nanoparticles were obtained.

[0047] (3) Preparation of ceramic membrane catalytic reactor

[0048] 1.5 g of FeVO4-FeCeO3 nanoparticles prepared in step (2), 30 g of red mud clay and 10 g of activated carbon were ground and sieved, then mixed uniformly, 1 g of PVA, 1 g of aluminum oxide, 55 g of magnesium oxide, 1.5 g of graphite powder and 0.5 g of PMA were added, then the mixture was added into a mold and pressure formed, and the ceramic membrane ligand after pressure holding was placed in a muffle furnace and calcined at 600℃ for 2 h to obtain a porous ceramic membrane catalytic reactor. For convenience, the ceramic membrane catalytic reactor is referred to as M1 hereinafter.

[0049] In the step (1), the distilled water can be 80-120 mL; the PEG200 can be replaced by PEG400, PEG600, which are liquid at room temperature, and PEG800-1000 can also be used, which is liquid at 75℃ reaction temperature, and the PEG amount can be 0.5-0.85 times of the amount of Ce(NO3)4. The amount of Ce(NO3)4, Fe(NO3)3 and sodium citrate can be 1.1: (0.9-1.1): (1.1-1.3) by mass ratio; the reaction temperature can be 60-90℃; and the reaction time can be 1-10h.

[0050] In the step (2), the amount of V2O5 and FeCeO3 used can be (0.25-0.5):1 by mass ratio; the temperature of the microwave chemical device can be 140-160℃, and the pressure can be 3.5-4.5MPa.

[0051] In the step (3), the amount of FeVO4-FeCeO3 nanoparticles, red mud clay, activated carbon, PVA, aluminum oxide, magnesium oxide, graphite powder and PMA can be (1-2):30:10:1: (1-2): (55-60): (1.5-2): (0.5-1) by mass ratio.

[0052] (4) Preparation of the membrane M2 catalytic reactor

[0053] According to the step (3), only Fe2O3 is used in the active component of the catalyst, and other preparation methods are the same as the step (3), the difference is that the membrane catalytic reactor for preparing Fe2O3 is prepared for comparison, and the obtained ceramic membrane catalytic reactor is recorded as M2.

[0054] Activity evaluation test

[0055] The catalyst is loaded in a fixed reaction bed, the activity evaluation length of the catalyst is 20cm, the inner diameter is 40mm, the loading amount of the catalyst is 105g each time, that is, the height of the catalyst is 10cm. The water / oil ratio (volume ratio) is 2.8:1, the space velocity is 1.0h -1 , the reaction temperature is 580℃, and the preheating temperature is 620℃. The concentration of the vinyl / isopropyl monomer is determined by GC, and the reaction liquid is collected. The catalytic activity of M1 and M2 is shown in the following table.

[0056] Table 1.1 Catalytic activity evaluation data table of M1

[0057] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 65.5 98.3 64.4 Divinylbenzene 64.8 98.0 63.5 p-Methylstyrene 67.5 99.2 67.0 p-tert-butylstyrene 63.4 98.4 62.4 α-Methylstyrene 63.7 98.9 63.0 m-Diisopropenebenzene 61.4 98.9 60.7 p-Diisopropylenebenzene 63.6 98.1 62.4

[0058] Table 1.2 Catalytic activity evaluation data table of M2

[0059] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 60.8 95.3 57.8 Divinylbenzene 60.1 94.7 56.9 p-Methylstyrene 62.8 95.9 60.2 p-tert-butylstyrene 58.7 95.1 55.8 α-Methylstyrene 59.1 95.6 56.4 m-Diisopropenebenzene 56.7 95.6 54.2 p-Diisopropylenebenzene 63.6 98.1 62.4

[0060] Stability evaluation test

[0061] The continuous activity evaluation test was carried out by using a plunger pump, and the temperature changes of each section of the preheater and the reactor were observed. When a large temperature change was found, the temperature setting parameters were adjusted to ensure that the temperature of the upper, middle and lower parts of the reactor did not exceed 580℃. During the experiment, the feed flow rate and temperature were recorded every 1h, and the sample was sampled and analyzed every 2h to evaluate the content of vinyltoluene. The evaluation lasted for 30 days.

[0062] The results show that the activity reduction rate of M1 is 1.1%, which is significantly lower than that of M2 of 7.6%, indicating that the use of ceramic membrane surface single atom catalysis can improve the catalytic activity and the stability of the catalyst, and the M1 membrane catalytic reactor material with stable framework structure has slower activity reduction and better stability. Example 2

[0063] In step (2) of Example 1, “100g of FeCeO3 sol prepared in step (1) (wherein the net content of FeCeO3 is 2.15g)” was used instead, and the rest was the same as Example 1. The catalytic activity of M1 is shown in the following table, and the catalytic activity of M2 is shown in Table 1.2.

[0064] Table 2 Catalytic activity evaluation data table of M1

[0065] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 42.3 95.1 40.2 Divinylbenzene 44.6 94.3 42.1 p-Methylstyrene 46.1 95.1 43.8 p-tert-butylstyrene 43.2 95.3 41.2 α-Methylstyrene 42.2 94.6 39.9 m-Diisopropenebenzene 41.5 95.9 39.8 p-Diisopropylenebenzene 41.8 94.1 39.3

[0066] The results show that the excessive filling of Ce atoms weakens the effect of the catalyst on the dehydrogenation synthesis of ethylbenzene / isopropylbenzene derivatives into vinyl / isopropyl monomers, and reduces the raw material conversion rate, the selectivity of special resin monomers and the yield of target products.

[0067] Stability evaluation test

[0068] The continuous activity evaluation test was carried out by using a plunger pump, and the temperature changes of each section of the preheater and the reactor were observed. When a large temperature change was found, the temperature setting parameters were adjusted to ensure that the temperature of the upper, middle and lower parts of the reactor did not exceed 580℃. During the experiment, the feed flow rate and temperature were recorded every 1h, and the sample was sampled and analyzed every 2h to evaluate the content of vinyltoluene. The evaluation lasted for 30 days.

[0069] The results show that the activity reduction rate of M1 is 3.3%, indicating that the excessive filling of Ce atoms affects the stability of the catalytic crystal structure, thereby reducing the stability of the catalyst. Example 3

[0070] In step (2) of Example 1, “0.4g of V2O5” was used instead, and the rest was the same as Example 1. The catalytic activity of M1 is shown in the following table, and the catalytic activity of M2 is shown in Table 1.2.

[0071] Table 3 Catalytic activity evaluation data table of M1

[0072] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 55.3 97.2 53.8 Divinylbenzene 54.6 97.5 53.2 p-Methylstyrene 57.5 97.7 56.2 p-tert-butylstyrene 53.3 98.5 52.5 α-Methylstyrene 53.6 98.3 52.7 m-Diisopropenebenzene 51.3 98.1 50.3

[0073] The results show that reducing the loading of V atoms reduces the catalytic area, resulting in reduced conversion of raw materials, monomer selectivity of special resins, and yield of target products.

[0074] Stability evaluation test

[0075] A continuous activity evaluation test was performed using a plunger pump to observe the temperature changes in each section of the preheater and reactor. When significant temperature changes were found, the temperature setting parameters were adjusted to ensure that the temperatures at the top, middle, and bottom of the reactor did not exceed 580°C. During the experiment, the feed flow rate and temperature were recorded every 1 h, and the sample was sampled and analyzed for vinyltoluene content every 2 h. The evaluation lasted for 30 days.

[0076] The results show that the activity reduction rate of M1 is 5.1%, and reducing the loading of V atoms will affect the stability of the catalytic material. Example 4

[0077] In step (2) of Example 1, "1 g V2O5" was used instead, and the other steps were the same as in Example 1. The catalytic activity of M1 is shown in the table below, and the catalytic activity of M2 is shown in Table 1.2.

[0078] Table 4 Catalytic activity evaluation data table of M1

[0079] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 62.3 99.3 61.9 Divinylbenzene 64.5 99.0 63.9 p-Methylstyrene 65.1 99.2 64.6 p-tert-butylstyrene 62.1 97.4 60.5 α-Methylstyrene 59.7 96.4 57.6 m-Diisopropenebenzene 59.2 97.8 57.9 p-Diisopropylenebenzene 60.1 96.9 58.2

[0080] The results show that increasing the loading of V atoms does not significantly enhance the effect of the catalyst on the dehydrogenation of ethylbenzene / cumene derivatives to synthesize vinyl / isopropyl monomers, and the special derivative raw materials have good catalytic performance.

[0081] Stability evaluation test

[0082] A continuous activity evaluation test was performed using a plunger pump to observe the temperature changes in each section of the preheater and reactor. When significant temperature changes were found, the temperature setting parameters were adjusted to ensure that the temperatures at the top, middle, and bottom of the reactor did not exceed 580°C. During the experiment, the feed flow rate and temperature were recorded every 1 h, and the sample was sampled and analyzed for vinyltoluene content every 2 h. The evaluation lasted for 30 days.

[0083] The results show that the activity reduction rate of M1 is only 1.9%. Example 5

[0084] In step (4) of Example 1, "1.25 g V2O5" was used instead, and the other steps were the same as in Example 1. The catalytic activity of M1 is shown in the table below, and the catalytic activity of M2 is shown in Table 1.2.

[0085] Table 5 Catalytic activity evaluation data table of M1

[0086] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 50.3 97.1 48.8 Divinylbenzene 54.1 97.3 52.6 p-Methylstyrene 51.3 98.1 50.3 p-tert-butylstyrene 53.5 97.3 52.1 α-Methylstyrene 50.4 96.6 48.7 m-Diisopropenebenzene 49.6 97.9 48.6 p-Diisopropylenebenzene 48.9 98.1 48.0

[0087] The results show that excessive increase of the loading of V atoms weakens the effect of the catalyst on the dehydrogenation of ethylbenzene / cumene derivatives to synthesize vinyl / isopropyl monomers, and the raw material conversion rate, the special resin monomer selectivity and the target product yield are reduced.

[0088] Stability evaluation test

[0089] The continuous activity evaluation test is carried out by using a plunger pump, and the temperature changes of each section of the preheater and the reactor are observed. When a large temperature change is found, the temperature setting parameters are adjusted to ensure that the temperature of the upper, middle and lower parts of the reactor does not exceed 580℃. During the experiment, the feed flow rate and temperature are recorded every 1h, and the vinyl toluene content of the sample is analyzed every 2h, and the evaluation time is 30 days.

[0090] The results show that the activity reduction rate of M1 is 3.9%, and excessive increase of the loading of V atoms affects the crystal structure of the catalyst, thereby causing the stability of the catalytic material to be significantly reduced.

[0091] The above examples 1-5 show that the mass ratio of the amount of V2O5 and FeCeO3 in step (2) is preferably in the range of (0.25-0.5): 1. Example 6

[0092] The "water to oil ratio (volume ratio) is changed to 2.9:1, the space velocity is 1.5h -1 , the reaction temperature is 590℃, the preheating temperature is 630℃, and the pressure is 1.06atm. The other conditions are the same as in example 1. The catalytic activities of M1 and M2 are shown in the following table.

[0093] Table 6.1 Catalytic activity evaluation data table of M1

[0094] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 56.1 98.1 55.0 Divinylbenzene 53.4 97.5 52.1 p-Methylstyrene 55.3 98.8 54.6 p-tert-butylstyrene 53.6 98.5 52.8 α-Methylstyrene 52.9 98.6 52.2 m-Diisopropenebenzene 52.4 98.7 51.7 p-Diisopropylenebenzene 51.6 97.7 50.4

[0095] Table 6.2 Catalytic activity evaluation data table of M2

[0096] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 51.4 94.8 48.7 Divinylbenzene 48.7 94.2 45.9 p-Methylstyrene 50.6 95.5 48.3 p-tert-butylstyrene 48.9 95.2 46.6 α-Methylstyrene 48.2 95.3 45.9 m-Diisopropenebenzene 47.7 95.4 45.5 p-Diisopropylenebenzene 46.9 94.4 44.3

[0097] The results show that increasing energy consumption to change the activity evaluation conditions does not significantly enhance the effect of the catalyst on the dehydrogenation of ethylbenzene / cumene derivatives to synthesize vinyl / isopropyl monomers, and the raw material conversion rate, the special resin monomer selectivity and the target product yield are reduced. The raw material conversion rate, the special resin monomer selectivity and the target product yield of M1 and M2 are also reduced.

[0098] Stability evaluation test

[0099] The continuous activity evaluation test was carried out by using a plunger pump, and the temperature changes of each section of the preheater and the reactor were observed. When a large temperature change was found, the temperature setting parameters were adjusted to ensure that the temperature of the upper, middle and lower parts of the reactor did not exceed 590°C. During the experiment, the feed flow rate and temperature were recorded every 1 h, and the sample was sampled and analyzed every 2 h to evaluate the content of vinyltoluene, and the evaluation time was 30 days.

[0100] The results show that the activity reduction rate of M1 is 5.1%, which is significantly lower than that of M2 of 8.7%. The severe reaction conditions can reduce the stability of the catalyst material, and the M1 membrane catalyst reactor material with a stable frame structure has a slower activity reduction. Example 7

[0101] The "catalyst activity evaluation length is 20 cm, the inner diameter is 40 mm, and the catalyst loading amount is 87 g per reaction, i.e. the catalyst height is 8 cm." was changed, and the other conditions were the same as in Example 1. The catalytic activities of M1 and M2 are shown in the following table.

[0102] Table 7.1 M1 catalytic activity evaluation data table

[0103] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 50.1 97.2 48.7 Divinylbenzene 49.7 97.5 48.5 p-Methylstyrene 51.5 97.7 50.3 p-tert-butylstyrene 52.1 98.5 51.3 α-Methylstyrene 48.8 98.3 48.0 m-Diisopropenebenzene 46.7 98.1 45.8 p-Diisopropylenebenzene 49.3 97.1 47.9

[0104] Table 7.2 M2 catalytic activity evaluation data table

[0105] Vinyl / isopropylene monomer A / % S / % Y / % Vinyltoluene 45.4 93.9 42.6 Divinylbenzene 45.1 94.2 42.4 p-Methylstyrene 46.8 94.4 44.2 p-tert-butylstyrene 47.4 95.2 45.1 α-Methylstyrene 44.1 95.0 41.9 m-Diisopropenebenzene 42.3 94.8 39.8 p-Diisopropylenebenzene 44.6 93.8 41.8

[0106] The results show that reducing the height of the membrane catalytic reactor weakens the effect of the catalyst on the dehydrogenation of ethylbenzene / cumene derivatives to synthesize vinyl / isopropyl monomers, and the raw material conversion rate, special resin monomer selectivity and target product yield are reduced. The raw material conversion rate, special resin monomer selectivity and target product yield of M2 also decrease.

[0107] Stability evaluation test

[0108] The continuous activity evaluation test was carried out by using a plunger pump, and the temperature changes of each section of the preheater and the reactor were observed. When a large temperature change was found, the temperature setting parameters were adjusted to ensure that the temperature of the upper, middle and lower parts of the reactor did not exceed 580°C. During the experiment, the feed flow rate and temperature were recorded every 1 h, and the sample was sampled and analyzed every 2 h to evaluate the content of vinyltoluene, and the evaluation time was 30 days.

[0109] The results show that the activity reduction rates of M1 and M2 are 17.9% and 22.6%, respectively, and the stability of the catalytic material is significantly reduced by reducing the height of the membrane catalytic reactor.

[0110] Those skilled in the art can easily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor, characterized in that The method comprises the following steps: (1) preparing FeCeO3 sol by sol-gel method Ce(NO3)4, Fe(NO3)3 and sodium citrate are dissolved in distilled water, and then liquid polyethylene glycol is added; the mixed solution is fully stirred and reacted in a microwave chemical device to obtain FeCeO3 sol; the polyethylene glycol is a pore-forming agent for FeCeO3 sol; the sodium citrate is used for adjusting the pH value of the reaction solution; the mass ratio of the amounts of Ce(NO3)4, Fe(NO3)3 and sodium citrate is 1.1: (0.9-1.1): (1.1-1.3); the reaction temperature is 60-90℃; and the reaction time is 1-10h; (2) preparing FeVO4-FeCeO3 nanoparticles by chemical deposition method V2O5 is dispersed in deionized water, and then the V2O5 suspension and the FeCeO3 sol prepared in step (1) are fully stirred and uniformly mixed, and then placed in a microwave chemical device for reaction under certain temperature and pressure; after acid washing, water washing, drying and calcination annealing, FeVO4-FeCeO3 nanoparticles are obtained; the mass ratio of the amounts of V2O5 and FeCeO3 used is (0.25-0.5):1; the temperature of the microwave chemical device is 140-160℃, and the pressure is 3.5-4.5MPa; (3) preparation of ceramic membrane catalytic reactor FeVO4-FeCeO3 nanoparticles, red mud clay and activated carbon prepared in step (2) are ground and sieved in a certain ratio, and then uniformly mixed, and then PVA, aluminum oxide, magnesium oxide, graphite powder and propylene glycol methyl ether acetate are added, and then the mixture is added into a mold for pressure forming to obtain a ceramic membrane ligand, and the ceramic membrane ligand after pressure maintaining is placed in a muffle furnace for high-temperature calcination to obtain a porous ceramic membrane catalytic reactor.

2. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (1), the amount of polyethylene glycol is 0.5-0.85 times the amount of Ce(NO3)4, and the amount of distilled water is 20-30 times the amount of Ce(NO3)4.

3. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (1), the temperature of the microwave chemical device is 75℃, and the time of the microwave chemical device is 2h.

4. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (2), the dispersion time of deionized water is 1h, the reaction time is 30min, and the stirring time is 30min.

5. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (2), the temperature of the microwave chemical device is 150℃, and the pressure of the microwave chemical device is 4.0MPa.

6. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (2), the calcination annealing temperature is 650-700℃.

7. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (3), the mass ratio of the amounts of FeVO4-FeCeO3 nanoparticles, red mud clay, activated carbon, PVA, aluminum oxide, magnesium oxide, graphite powder and propylene glycol methyl ether acetate is (1-2):30:10:1:(1-2):(55-60):(1.5-2):(0.5-1).

8. The method for preparing FeVO4-FeCeO3 nanoparticle doped ceramic membrane catalytic reactor according to claim 1, characterized in that: In step (3), the calcination temperature of the muffle furnace is 600℃, and the time is 2h.