Titanium silicalite molecular sieve catalyst and preparation method thereof

Abstract

The invention relates to a titanium silicalite molecular sieve catalyst and a preparation method, and belongs to the field of catalyst preparation, and the preparation method comprises the following steps: S1, adding a silicon source: adding deionized water into a reaction container, then dropwise adding the silicon source into the deionized water, slowly stirring, and continuously stirring for 1-2 hours after dropwise adding is completed, so that the silicon source is fully hydrolyzed to form a uniform silicic acid solution; s2, adding a titanium source: slowly dropwise adding the titanium source into the silicate solution under vigorous stirring, meanwhile, adding a complexing agent to react with the titanium source, and continuously stirring for 1-2 hours to form a stable titanium complex. The acetylacetone is added into the titanium source, the acetylacetone and titanium can form a stable complex, and the complex can slowly release titanium ions in the hydrolysis process, so that the hydrolysis speed of the titanium source is slowed down, the hydrolysis speed of the titanium source is better matched with the hydrolysis speed of a silicon source, and the dispersity of titanium in a molecular sieve framework is improved; the agglomeration of titanium atoms is effectively avoided, so that the activity of the catalyst is enhanced.

Description

Technical Field

[0001] The invention relates to a titanium silicon molecular sieve catalyst and a preparation method thereof, belonging to the field of catalyst preparation. Background Art

[0002] Titanium silicate molecular sieve catalyst is a type of molecular sieve material with silicon and titanium as the main components. It is a material with good performance in catalytic reactions and is usually used for redox reactions, especially in the fields of environmental protection and energy conversion, such as catalytic degradation of pollutants and catalytic organic reactions.

[0003] However, in the process of synthesis and preparation of existing titanium silicon molecular sieve catalysts, it is difficult to effectively control the dispersion uniformity of titanium species and silicon species in the precursor solution, and it is also impossible to effectively slow down the hydrolysis rate of the titanium source to make it more compatible with the hydrolysis rate of the silicon source. Therefore, titanium atoms are very likely to agglomerate, and the poor dispersion uniformity of titanium species and silicon species will greatly affect the assembly of the molecular sieve framework structural units, thereby reducing the catalytic performance of the final titanium silicon molecular sieve. Moreover, in the process of synthesis and preparation of existing titanium silicon molecular sieve catalysts, it is impossible to effectively improve the stability of the molecular sieve framework structure. Therefore, under high-temperature reaction conditions, the crystal structure of the titanium silicon molecular sieve may change, resulting in the collapse of the framework, thereby inactivating the catalyst and limiting its application in some high-temperature catalytic reactions. Therefore, we have made improvements on this and proposed a titanium silicon molecular sieve catalyst and a preparation method. Summary of the invention

[0004] (I) The technical problem to be solved by the present invention is that it is difficult to effectively control the dispersion uniformity of titanium species and silicon species in the precursor solution during the synthesis and preparation process of the existing titanium silicon molecular sieve catalyst, and it is also impossible to effectively slow down the hydrolysis rate of the titanium source to make it more compatible with the hydrolysis rate of the silicon source; and it is also impossible to effectively improve the stability of the molecular sieve framework structure.

[0005] (II) Technical solution In order to achieve the above-mentioned object of the invention, the present invention provides a titanium silicon molecular sieve catalyst, which is prepared by the following steps: S1: Adding silicon source: Add deionized water into the reaction container, then drop the silicon source into the deionized water and stir slowly. After the dropwise addition is completed, continue stirring for 1 to 2 hours to fully hydrolyze the silicon source to form a uniform silicic acid solution; S2: Adding titanium source: Slowly adding titanium source to the silicate solution under vigorous stirring, at the same time, adding complexing agent to react with the titanium source, and continuing stirring for 1 to 2 hours to form a stable titanium complex; S3: preparing sol: slowly adding the template to the solution in S2, adding fatty acid and small molecule organic amine at the same time, and continuously stirring, then adding organosilane, sodium nitrate and lanthanum nitrate, and continuously stirring for 1 hour to form a uniform sol; S4: crystallization treatment: the sol in S3 is transferred to an autoclave for crystallization treatment, and a crystallized product with a regular crystal structure is gradually formed; S5: Post-treatment: After the crystallization treatment is completed, the reactor is opened, and the crystallized product is allowed to cool naturally to room temperature, and then the crystallized product is filtered, washed and dried through a processing device to remove excess templates and impurities, and a dry molecular sieve precursor is obtained; S6: Calcination treatment: The dried molecular sieve precursor is placed in a muffle furnace for calcination to remove the organic template and stabilize the crystal structure to form the final structure of the titanium silicon molecular sieve.

[0006] Among them, the silicon source in S1 is tetraethyl orthosilicate, the titanium source in S2 is tetrabutyl titanate, the complexing agent in S2 is acetylacetone, the template agent in S3 is tetrapropylammonium hydroxide, the fatty acid in S3 is stearic acid, the small molecule organic amine in S3 is triethanolamine, and the organic silane in S3 is trimethylsilane.

[0007] The molar ratio of tetraethyl orthosilicate: tetrabutyl titanate: tetrapropylammonium hydroxide: deionized water: fatty acid: acetylacetone: organic silane: sodium nitrate: lanthanum nitrate: small molecule organic amine is 1:0.1:0.1:20:0.05:0.02:0.02:0.01:0.01:0.05.

[0008] Wherein, the tetraethyl orthosilicate and tetrabutyl titanate in S2 undergo hydrolysis reaction in deionized water at a reaction temperature of 0°C to 30°C.

[0009] Among them, the hydrolysis reaction equation in S2 is: Si(OC2H5)4+4H2O→Si(OH)4+4C2H5OH. The generated silicic acid will further condense to form a silicon-oxygen tetrahedral structure.

[0010] Among them, the pH value of the mixed solution in S3 is 9~11.

[0011] Among them, the reactor in S4 is a stainless steel autoclave, and the crystallization treatment in S4 is divided into pre-crystallization treatment and secondary crystallization treatment; pre-crystallization treatment: pre-crystallization is carried out at 100°C-150°C, and the pre-crystallization time is 0.5~8 hours; secondary crystallization treatment: hydrothermal crystallization is continued at 150°C-190°C for 4~96 hours.

[0012] In the washing step in S5, deionized water, a diluted acid solution, a diluted alkali solution and ethanol are used to perform multi-stage washing on the crystallized product, wherein the diluted acid solution is diluted hydrochloric acid, and the diluted alkali solution is diluted sodium hydroxide solution.

[0013] Among them, the roasting temperature of the muffle furnace in S6 is 550~600℃, the roasting time is 6~8 hours, and the heating rate is controlled at 1℃~2℃ / minute.

[0014] Among them, the processing equipment used in S5 is a multifunctional processing equipment, including: The top surface of the bottom plate is provided with a hydraulic rod, the top of the hydraulic rod is fixedly connected with a mounting plate, the hydraulic rods are symmetrically distributed on both sides of the top of the bottom plate, the hydraulic rods correspond to the mounting plates one by one, an automatic flipping assembly is installed on the mounting plate on one side, the end of the processing cylinder is fixedly connected with a sealing ring, a card slot is provided on the processing cylinder, a multifunctional stirring assembly is installed in the processing cylinder, a sleeve is provided on the processing cylinder, a fixing pipe is fixedly connected to the sleeve, a support rod is welded and fixed in the sleeve, a second filter plate is welded and fixed on the support rod, the second filter plate is slidably connected in the processing cylinder, a positioning slot is penetrated through the second filter plate, a threaded rod is rotatably connected to the sleeve, a reset spring is welded and fixed on the outer wall of the sleeve, a clamping rod is welded and fixed on the reset spring, the clamping rod penetrates and is slidably connected to the sleeve, and the end of the clamping rod is clamped and connected in the clamping slot.

[0015] Wherein, the automatic flipping component includes a first servo motor and a first air guide tube, which are both welded and fixed on a mounting plate on one side, a turntable is welded and fixed on the output shaft of the first servo motor, a limit plate and a guide rod are welded and fixed on the turntable, the first air guide tube is rotatably connected to the first diverter tube through a bearing, a guide plate is welded and fixed on the first diverter tube, a guide groove is provided on the guide plate, the first diverter tube is connected to the second diverter tube, the second diverter tube is connected to the third diverter tube, the third diverter tube and the fixed tube are both equipped with solenoid valves, and the end of the third diverter tube is fixedly connected to the middle part of the side end of the processing cylinder.

[0016] Among them, a groove is provided on the limiting plate, the first diverter tube is connected to the center part of the guide plate, the side end face of the guide plate is arc-shaped, the side end face of the guide plate is in contact with the side end face of the limiting plate, four guide grooves are provided, and the four guide grooves are distributed at equal angles on the guide plate, the first diverter tube is connected to the middle part of the second diverter tube, and the third diverter tube is symmetrically distributed on both sides of the second diverter tube.

[0017] Wherein, the multifunctional stirring assembly includes a second servo motor and a stirring rod, the second servo motor is welded and fixed on the outer wall of the processing cylinder, a first gear is welded and fixed on the output shaft of the second servo motor, a second gear is meshed and connected to the first gear, a delivery pipe is welded and fixed on the second gear, one end of the delivery pipe is rotatably connected to the second air guide pipe through a sealed bearing, the other end of the delivery pipe is rotatably connected in the processing cylinder, the second air guide pipe is welded and fixed to the mounting plate on the other side, a through hole is opened on the delivery pipe, a first filter plate is welded and fixed in the through hole, a push plate is welded and fixed on the delivery pipe, and the inner wall of the processing cylinder is rotatably connected to a connecting ring through a bearing.

[0018] Among them, there are four groups of through holes, which are distributed on the conveying pipe at equal angles, and each group of through holes is equidistantly distributed on the conveying pipe. The through holes correspond one to one with the first filter plate, and the push plate is arranged in the central part of the processing cylinder, and the push plate is elliptical as a whole.

[0019] Among them, the connecting ring is symmetrically distributed on both sides of the processing cylinder, and a scraper rod is welded and fixed on the inner wall of the connecting ring. The scraper rods are distributed at equal angles in the connecting ring, and a rotating cylinder is welded and fixed on the scraper rod. The rotating cylinder is rotatably connected to the connecting cylinder through a bearing, and a sealing ring is fixedly connected in the connecting cylinder, and a sliding rod is welded and fixed on the inner wall of the connecting cylinder, and a connecting spring is welded and fixed in the connecting cylinder, and a connecting plate is welded and fixed on the connecting spring, and a driven rod is rotatably connected on the connecting plate, and the driven rod and the connecting plate are both slidably connected in the connecting cylinder, and a sliding groove is provided on the driven rod, and the end of the sliding rod is limitedly slidably connected in the sliding groove, and the sliding groove is spiral.

[0020] Among them, a support plate is welded and fixed on the driven rod, a slider is connected with a limited sliding connection in the support plate, one end of the stirring rod is hinged on the slider, the other end of the stirring rod is hinged on the scraper rod, a positioning rod is welded and fixed on the connecting tube, a threaded hole is opened in the positioning rod, the positioning rod is limited and slidably connected in the positioning groove, the threaded rod is threadedly connected in the threaded hole, the driven rod is fixed to the center of the support plate, the support plate is in a "cross" shape as a whole, the cross section of the slider is in a "T" shape, four groups of sliders are arranged, the four groups of sliders are distributed on the support plate at equal angles, each group of sliders is equidistantly distributed on the support plate, the sliders correspond to the stirring rods one by one, and the cross sections of the positioning rod and the positioning groove are both rectangular.

[0021] Among them, the sleeve is symmetrically distributed on both sides of the processing cylinder, the sleeve corresponds one-to-one with the second filter plate through the support rod, the connecting ring and the scraper rod are both fitted with the second filter plate, the side end surface of the second filter plate is fitted with the inner wall of the processing cylinder, the clamping rod is symmetrically distributed on both sides of the sleeve, and the clamping rod corresponds one-to-one with the clamping groove.

[0022] Among them, an insulation box is welded and fixed on the top surface of the bottom plate, and a third air duct is connected to the insulation box, and a rubber hose is connected to the third air duct, and the third air duct is symmetrically distributed on both sides of the insulation box, and an air pump is installed on the third air duct on one side, and the third air duct corresponds to the rubber hose one by one, the rubber hose on one side is connected to the first air duct, and the rubber hose on the other side is connected to the second air duct, and a filter frame, a dehumidification mesh plate and an activated carbon mesh plate are slidably connected through the insulation box, and an electric heating pipe is installed in the insulation box, and a magnetic cover frame is magnetically adsorbed on the top surface of the insulation box, and the top of the filter frame, the top of the dehumidification mesh plate and the top of the activated carbon mesh plate are all slidably connected in the filter frame, and the electric heating pipes are equidistantly distributed in the insulation box.

[0023] Beneficial Effects The titanium silicon molecular sieve catalyst and preparation method provided by the present invention have the following beneficial effects: 1. By adding acetylacetone to the titanium source, acetylacetone can form a stable complex with titanium. This complex can slowly release titanium ions during the hydrolysis process, thereby slowing down the hydrolysis rate of the titanium source, making it more compatible with the hydrolysis rate of the silicon source, and thus improving the dispersion of titanium in the molecular sieve framework; and adding fatty acids to the synthesis system can adjust the polarity and viscosity of the synthesis system, reduce the surface tension of the system, make the titanium source and the silicon source better dispersed in the solution, promote the uniform entry of titanium atoms into the molecular sieve framework, thereby optimizing the pore structure, and further improving the dispersion of the titanium active center, effectively The agglomeration of titanium atoms is avoided, thereby enhancing the activity of the catalyst; and by adopting a gradient crystallization temperature, the embedding process of titanium atoms can be effectively controlled, further improving the dispersion of titanium active centers; and in the synthesis process, by mixing tetrapropylammonium hydroxide with small-molecule organic amines, the small-molecule organic amines can enter the micropores and smaller mesopore areas of the molecular sieve, while tetrapropylammonium hydroxide mainly guides the formation of micropores. The synergistic effect of the two can enrich the pore structure, increase the proportion and distribution uniformity of mesopores, and further optimize the pore structure of the molecular sieve and the dispersion of titanium active centers.

[0024] 2. By adding organosilane during the synthesis process, the silaneoxy groups in the organosilane can undergo a condensation reaction with the silanol groups of the titanium silicalite molecular sieve to form a coating of organosilane on the surface of the molecular sieve, thereby increasing the hydrophobicity of the molecular sieve and reducing the damage to the molecular sieve structure by polar molecules such as water molecules. At the same time, the pore structure and pore size are adjusted to improve the affinity and selectivity of the catalyst for organic reactants, so that it performs better in some catalytic processes involving organic reactions, thereby improving the chemical stability of the catalyst; at the same time, the combination with lanthanum nitrate can further optimize the skeleton structure of the molecular sieve, enabling it to withstand higher temperatures and improve the activity and selectivity of the catalyst.

[0025] 3. Through the first servo motor, the limit plate and guide rod on the turntable can be driven to move stably. Combined with the guide grooves on the guide plate, the third diversion pipe can be used to drive the processing cylinder to automatically and stably flip intermittently, and then the crystallization product in the processing cylinder can be automatically flipped, thereby achieving efficient and uniform mixing of the crystallization product and the washing solution, avoiding the accumulation of a large amount of crystallization products, resulting in the problem that the crystallization products accumulated inside cannot be in comprehensive and uniform contact with the washing solution, effectively improving the washing efficiency and washing effect of the crystallization product, and avoiding incomplete washing affecting the final preparation quality of the titanium silicon molecular sieve catalyst.

[0026] 4. Through the continuous rotation of the push plate, combined with the elasticity of the connecting spring, the support plates on the driven rods on both sides can be pushed to perform automatic and stable reciprocating motion. At the same time, under the guidance of the sliding rod and the sliding groove, the support plates in the reciprocating motion can be driven to automatically reciprocate, and then the stirring rods on each slider can be driven to automatically rotate and reciprocate, achieving efficient and uniform mixing of the crystallized product and the washing solution, effectively improving the washing efficiency and washing effect of the crystallized product. This makes up for the problem that the existing stirring mechanism can only stir in a single direction at a fixed position, with poor mixing effect and low mixing rate.

[0027] 5. By setting up the third air duct, rubber hose and air pump, combined with the delivery pipe and the third diversion pipe, air can circulate inside the treatment barrel after the washing work is completed, and under the joint action of the filter frame, dehumidification mesh plate, activated carbon mesh plate and electric heating tube, air filtering, dehumidification, purification and heating can be achieved to avoid environmental pollution and heat loss, and combined with the automatic flipping component and the multi-functional stirring component, the crystallized product after washing can be comprehensively and efficiently dried, realizing the integrated processing of the crystallized product, further improving the processing efficiency, and increasing the diversity and convenience of the treatment device. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0029] Figure 1 It is a schematic diagram of the process of the present invention; Figure 2 This is a schematic diagram of the three-dimensional structure of the treatment tube of the present invention; Figure 3It is a schematic diagram of the connection structure between the mounting plate and the first servo motor of the present invention; Figure 4 It is a schematic diagram of the connection structure between the turntable and the limit plate of the present invention; Figure 5 This is a schematic diagram of the connection structure between the first shunt pipe and the guide plate of the present invention; Figure 6 This is a schematic diagram of the connection structure between the first gear and the second gear of the present invention; Figure 7 It is a schematic diagram of the connection structure between the delivery pipe and the push plate of the present invention; Figure 8 For the present invention Figure 7 The enlarged structural diagram at A in the middle; Fig. 9 This is a schematic diagram of the connection structure between the first filter plate and the through hole of the present invention; Fig.10 This is a schematic diagram of the connection structure between the treatment cylinder and the sealing ring of the present invention; Fig.11 For the present invention Fig.10 The enlarged structural diagram at B in the middle; Fig.12 It is a schematic diagram of the connection structure of the connection ring and the scraper rod of the present invention; Fig.13 This is a schematic diagram of the connection structure of the scraper rod and the stirring rod of the present invention; Fig.14 This is a schematic diagram of the connection structure between the slider and the stirring rod of the present invention; Fig.15 This is a schematic diagram of the main cross-sectional structure of the connecting tube of the present invention; Fig.16 This is a schematic diagram of the top-sectional structure of the connecting tube of the present invention; Fig.17 It is a schematic diagram of the connection structure between the temperature-isolating box and the magnetic cover frame of the present invention; Fig.18 It is a schematic diagram of the connection structure of the temperature insulation box and the electric heating tube of the present invention.

[0030] In the figure: 1, bottom plate; 2, hydraulic rod; 3, mounting plate; 4, automatic flip assembly; 401, first servo motor; 402, turntable; 403, limit plate; 404, guide rod; 405, first air duct; 406, first shunt pipe; 407, guide plate; 408, guide groove; 409, second shunt pipe; 410, third shunt pipe; 5, treatment cylinder; 6, sealing ring; 7, card slot; 8, multi-function stirring assembly; 801, second servo motor; 802, first gear; 803, second gear; 804, delivery pipe; 805, second air duct; 806, first filter plate; 807, push plate; 808, connecting ring; 809, scraper rod; 810, turntable Moving cylinder; 811, connecting cylinder; 812, sealing ring; 813, sliding rod; 814, connecting spring; 815, connecting plate; 816, driven rod; 817, sliding groove; 818, supporting plate; 819, sliding block; 820, stirring rod; 821, positioning rod; 822, threaded hole; 823, through hole; 9, sleeve; 10, fixing tube; 11, supporting rod; 12, second filter plate; 13, positioning groove; 14, threaded rod; 15, reset spring; 16, clamping rod; 17, temperature insulation box; 18, third air guide tube; 19, rubber hose; 20, air pump; 21, filter frame; 22, dehumidification screen plate; 23, activated carbon screen plate; 24, electric heating tube; 25, magnetic cover frame. DETAILED DESCRIPTION

[0031] The specific implementation of the present invention is further described in detail below in conjunction with the accompanying drawings and examples of the specification. The following examples are only used to illustrate the present invention, but cannot be used to limit the scope of the present invention.

[0032] Embodiment 1: like Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 , Figure 6 , Figure 7 , Figure 8 , Fig. 9 , Fig.10 , Fig.11 , Fig.12 , Fig.13 , Fig.14 , Fig.15 and Fig.16 As shown, this embodiment provides a titanium silicon molecular sieve catalyst, which is prepared by the following steps: S1: Adding silicon source: Add deionized water into the reaction vessel, then drop ethyl orthosilicate into the deionized water and stir slowly. After the dropwise addition is completed, continue stirring for 1 hour to allow the ethyl orthosilicate to be fully hydrolyzed to form a uniform silicic acid solution; S2: Adding titanium source: Tetrabutyl titanate is slowly added dropwise to the silicate solution under vigorous stirring. At the same time, acetylacetone is added to react with tetrabutyl titanate and stirring is continued for 1 hour to form a stable titanium complex; S3: preparing sol: slowly adding tetrapropylammonium hydroxide to the solution in S2, adding stearic acid and triethanolamine at the same time, and continuously stirring, then adding trimethylsilane, sodium nitrate and lanthanum nitrate, controlling the pH value to 9, and continuously stirring for 1 hour to form a uniform sol; The molar ratio of ethyl orthosilicate: tetrabutyl titanate: tetrapropylammonium hydroxide: deionized water: fatty acid: acetylacetone: organic silane: sodium nitrate: lanthanum nitrate: small molecule organic amine is 1:0.1:0.1:20:0.05:0.02:0.02:0.01:0.01:0.05; Ethyl orthosilicate and tetrabutyl titanate undergo hydrolysis in deionized water at a reaction temperature of 0°C to 30°C. The hydrolysis reaction equation is: Si(OC2H5)4+4H2O→Si(OH)4+4C2H5OH. The generated silica will further condense to form a silicon-oxygen tetrahedral structure. S4: Crystallization treatment: The sol in S3 is transferred to a stainless steel autoclave for crystallization treatment, firstly pre-crystallization is carried out at a temperature of 100°C for 8 hours; then hydrothermal crystallization is continued at a temperature of 150°C for 96 hours, and secondary crystallization is carried out to gradually form a crystallized product with a regular crystal structure; S5: Post-treatment: After the crystallization treatment is completed, the reactor is opened, and the crystallized product is allowed to cool naturally to room temperature, and then the crystallized product is filtered, washed and dried by a treatment device, wherein the crystallized product is washed in multiple stages with deionized water, a diluted acid solution, a diluted alkali solution and ethanol, wherein the diluted acid solution is a diluted hydrochloric acid, and the diluted alkali solution is a diluted sodium hydroxide solution, to remove excess templates and impurities, and obtain a dry molecular sieve precursor; S6: Calcination treatment: The dried molecular sieve precursor is placed in a muffle furnace for calcination at a temperature of 550°C for 8 hours and a heating rate of 2°C / min to remove the organic template and stabilize the crystal structure to form the final structure of the titanium silicon molecular sieve.

[0033] The processing equipment used in S5 is a multifunctional processing equipment, including: A bottom plate 1 and a processing cylinder 5, a hydraulic rod 2 is fixedly installed on the top surface of the bottom plate 1, and a mounting plate 3 is fixedly connected to the top of the hydraulic rod 2. The hydraulic rods 2 are symmetrically distributed on both sides of the top of the bottom plate 1, and the hydraulic rods 2 correspond to the mounting plates 3 one by one. An automatic flip assembly 4 is installed on the mounting plate 3 on one side, and a sealing ring 6 is fixedly connected to the end of the processing cylinder 5. A card slot 7 is opened on the processing cylinder 5, and a multifunctional stirring assembly 8 is installed in the processing cylinder 5. A sleeve 9 is sleeved on the processing cylinder 5, and a fixed pipe 10 is fixedly connected to the sleeve 9. A support rod 11 is welded and fixed in the sleeve 9, and a second filter plate 12 is welded and fixed on the support rod 11. The second filter plate 12 is slidably connected in the processing cylinder 5, and a positioning groove 13 is opened through the second filter plate 12. A threaded rod 14 is rotatably connected to the sleeve 9, and the outer wall of the sleeve 9 is welded and fixed There is a reset spring 15, on which a clamping rod 16 is welded and fixed, the clamping rod 16 penetrates and is slidably connected to the sleeve 9, the end of the clamping rod 16 is clamped and connected in the clamping groove 7, and the automatic flipping component 4 can drive the processing tube 5 to automatically and stably flip intermittently, so as to automatically flip the crystallized product in the processing tube 5, thereby realizing efficient and uniform mixing of the crystallized product and the washing solution, avoiding the accumulation of a large amount of crystallized product, resulting in the problem that the crystallized product accumulated inside cannot be in comprehensive and uniform contact with the washing solution; combined with the multifunctional stirring component 8, the crystallized product and the washing solution can be efficiently and evenly mixed, and multi-stage washing and drying treatments can be performed, thereby realizing the integrated processing of the crystallized product, further improving the processing efficiency, and increasing the diversity and convenience of the processing device.

[0034] Embodiment 2: The solution in Example 1 is further introduced below in combination with a specific working method, as described below: like Figure 3 , Figure 4 and Figure 5As shown, as a preferred embodiment, on the basis of the above method, further, the automatic flip assembly 4 includes a first servo motor 401 and a first air guide tube 405, the first servo motor 401 and the first air guide tube 405 are welded and fixed on the mounting plate 3 on one side, a turntable 402 is welded and fixed on the output shaft of the first servo motor 401, a limit plate 403 and a guide rod 404 are welded and fixed on the turntable 402, and the first air guide tube 405 is rotatably connected to the first diversion tube 4 through a bearing. 06, a guide plate 407 is welded and fixed on the first shunt pipe 406, a guide groove 408 is provided on the guide plate 407, the first shunt pipe 406 is connected to the second shunt pipe 409, the second shunt pipe 409 is connected to the third shunt pipe 410, a filter screen is fixed at the end of the third shunt pipe 410, the third shunt pipe 410 and the fixed pipe 10 are both equipped with a solenoid valve, the end of the third shunt pipe 410 is fixedly connected to the middle part of the side end of the treatment cylinder 5, and a groove is provided on the limit plate 403 , the first shunt pipe 406 is connected to the central part of the guide plate 407, the side end face of the guide plate 407 is in an arc shape, the side end face of the guide plate 407 is in contact with the side end face of the limiting plate 403, four guide grooves 408 are provided, and the four guide grooves 408 are distributed at equal angles on the guide plate 407, the first shunt pipe 406 is connected to the middle part of the second shunt pipe 409, and the third shunt pipe 410 is symmetrically distributed on both sides of the second shunt pipe 409. The limiting plate 403 and the guide rod 404 on the turntable 402 can be driven to move stably through the first servo motor 401. Combined with the guide grooves 408 on the guide plate 407, the third shunt pipe 410 can drive the processing cylinder 5 to automatically and stably turn over intermittently, so that the crystallized product in the processing cylinder 5 can be automatically turned over, thereby realizing efficient and uniform mixing of the crystallized product and the washing solution, effectively improving the washing efficiency and washing effect of the crystallized product, and avoiding incomplete washing affecting the final preparation quality of the titanium silicon molecular sieve catalyst.

[0035] like Figure 2 , Figure 3 , Figure 6 , Figure 7 , Fig. 9 and Fig.10As shown, as a preferred embodiment, on the basis of the above method, further, the multifunctional stirring assembly 8 includes a second servo motor 801 and a stirring rod 820, the second servo motor 801 is welded and fixed on the outer wall of the processing tube 5, the first gear 802 is welded and fixed on the output shaft of the second servo motor 801, the first gear 802 is meshed and connected with the second gear 803, the second gear 803 is welded and fixed with a delivery pipe 804, one end of the delivery pipe 804 is rotatably connected to the second air guide pipe 805 through a sealed bearing, the other end of the delivery pipe 804 is rotatably connected in the processing tube 5, the second air guide pipe 805 is welded and fixed to the mounting plate 3 on the other side, a through hole 823 is opened in the delivery pipe 804, the first filter plate 806 is welded and fixed in the through hole 823, and the delivery pipe 804 is welded A push plate 807 is fixed, and the inner wall of the processing cylinder 5 is rotatably connected to a connecting ring 808 through a bearing. Four groups of through holes 823 are arranged, and the four groups of through holes 823 are distributed at equal angles on the delivery pipe 804. Each group of through holes 823 is equidistantly distributed on the delivery pipe 804. The through holes 823 correspond to the first filter plate 806 one by one. The push plate 807 is arranged in the central part of the processing cylinder 5. The push plate 807 is elliptical as a whole. A solenoid valve is installed on the delivery pipe 804. Through the through holes 823 on the delivery pipe 804, combined with the third air guide pipe 18, the rubber hose 19 and the air pump 20, air can circulate inside the processing cylinder 5 after the washing work is completed, and combined with the heated circulating air, the washed crystallized product can be comprehensively and efficiently dried, thereby realizing the integrated processing of the crystallized product.

[0036] like Fig.10 , Fig.11 , Fig.12 , Fig.13 , Fig.14 , Fig.15 and Fig.16As shown, as a preferred embodiment, on the basis of the above-mentioned method, further, the connecting rings 808 are symmetrically distributed on both sides of the inside of the processing cylinder 5, and the scraper rods 809 are welded and fixed on the inner wall of the connecting ring 808. The scraper rods 809 are equiangularly distributed in the connecting ring 808. A rotating cylinder 810 is welded and fixed on the scraper rods 809. The rotating cylinder 810 is rotatably connected to the connecting cylinder 811 through a bearing. A sealing ring 812 is fixedly connected to the connecting cylinder 811. A sliding rod 813 is welded and fixed on the inner wall of the connecting cylinder 811. A connecting spring 814 is welded and fixed in the connecting cylinder 811. The connecting spring 814 is welded and fixed in the connecting cylinder 811. 4 is welded and fixed with a connecting plate 815, and a driven rod 816 is rotatably connected to the connecting plate 815. The driven rod 816 and the connecting plate 815 are both slidably connected in the connecting cylinder 811. A sliding groove 817 is provided on the driven rod 816. The end of the sliding rod 813 is limitedly slidably connected in the sliding groove 817. The sliding groove 817 is spiral. A supporting plate 818 is welded and fixed on the driven rod 816. A slider 819 is limitedly slidably connected in the supporting plate 818. One end of the stirring rod 820 is hinged on the slider 819, and the other end of the stirring rod 820 is hinged on the scraper rod 809. A positioning rod 821 is fixed to the support plate 818, a threaded hole 822 is provided in the positioning rod 821, the positioning rod 821 is limitedly slidably connected in the positioning groove 13, the threaded rod 14 is threadedly connected in the threaded hole 822, the driven rod 816 is fixed to the center of the support plate 818, the support plate 818 is in a "cross" shape as a whole, the cross section of the slider 819 is in a "T" shape, the slider 819 is provided with four groups, the four groups of sliders 819 are distributed on the support plate 818 at equal angles, each group of sliders 819 is equidistantly distributed on the support plate 818, the sliders 819 correspond one to one with the stirring rod 820, the cross section of the positioning rod 821 and the positioning The cross-section of the grooves 13 is rectangular. Through the continuous rotation of the push plate 807 and the elasticity of the connecting spring 814, the support plates 818 on the driven rods 816 on both sides can be pushed to perform automatic and stable reciprocating motion. At the same time, under the guidance of the sliding rod 813 and the sliding groove 817, the support plates 818 can be driven to automatically rotate back and forth during the reciprocating motion, and then the stirring rods 820 on each slider 819 can be driven to automatically rotate and reciprocate and retract, thereby achieving efficient and uniform mixing of the crystallization product and the washing solution, and effectively improving the washing efficiency and washing effect of the crystallization product.

[0037] like Figure 2 , Figure 7 , Figure 8 and Fig.10As shown, as a preferred embodiment, on the basis of the above method, further, the sleeve 9 is symmetrically distributed on both sides of the processing cylinder 5, the sleeve 9 corresponds one-to-one with the second filter plate 12 through the support rod 11, the connecting ring 808 and the scraper rod 809 are both in contact with the second filter plate 12, the side end surface of the second filter plate 12 is in contact with the inner wall of the processing cylinder 5, the clamping rod 16 is symmetrically distributed on both sides of the sleeve 9, the clamping rod 16 corresponds one-to-one with the clamping groove 7, and the cooperation of the clamping rod 16 and the clamping groove 7 can conveniently complete the disassembly and installation of the sleeve 9, so that the crystallization product can be loaded and unloaded conveniently and stably, which effectively improves the processing efficiency.

[0038] like Figure 2 , Fig.17 and Fig.18 As shown, as a preferred embodiment, on the basis of the above-mentioned method, further, a heat-insulating box 17 is welded and fixed on the top surface of the bottom plate 1, and a third air pipe 18 is connected to the heat-insulating box 17, and a rubber hose 19 is connected to the third air pipe 18. The third air pipes 18 are symmetrically distributed on both sides of the heat-insulating box 17, and an air pump 20 is installed on the third air pipe 18 on one side. The third air pipe 18 corresponds to the rubber hose 19 one by one. The rubber hose 19 on one side is connected to the first air pipe 405, and the rubber hose 19 on the other side is connected to the second air pipe 805. The heat-insulating box 17 is penetrated by a sliding connection. There are a filter frame 21, a dehumidification mesh plate 22 and an activated carbon mesh plate 23, an electric heating tube 24 is installed in the insulation box 17, and a magnetic cover frame 25 is magnetically adsorbed and connected to the top surface of the insulation box 17. The top of the filter frame 21, the top of the dehumidification mesh plate 22 and the top of the activated carbon mesh plate 23 are all slidably connected in the filter frame 21, and the electric heating tubes 24 are equidistantly distributed in the insulation box 17. Under the joint action of the filter frame 21, the dehumidification mesh plate 22, the activated carbon mesh plate 23 and the electric heating tube 24, combined with the circulation of air, it can realize the filtering, dehumidification, purification and heating of the air, avoiding environmental pollution and heat loss.

[0039] Embodiment 3: The schemes in Example 1 and Example 2 are further introduced below in combination with specific working methods, as described below for details: Specifically, when the multifunctional processing equipment for the titanium silicon molecular sieve catalyst and preparation method is in use: first, the staff can pull the clamping rods 16 on both sides of the upper sleeve 9 until the clamping rods 16 move out of the clamping grooves 7 on the processing tube 5. At the same time, another staff can rotate the threaded rod 14 on the upper sleeve 9. Under the action of the threaded rotation of the threaded rod 14, it can move out of the threaded hole 822 on the positioning rod 821. At this time, the disassembly and separation of the upper sleeve 9 can be completed, and the separation between the sleeve 9 and the multifunctional stirring assembly 8 can be completed. Then the staff can transport the crystallized product after the crystallization treatment to the processing tube 5. At this time, under the action of the second filter plate 12 inside the lower sleeve 9, the crystallized product after the crystallization treatment can be filtered, and the waste liquid is discharged through the fixed pipe 10 on the lower sleeve 9. After discharge, the solenoid valve on the lower fixed pipe 10 can be closed.

[0040] Then, through the same operation, the clamping rods 16 on both sides of the upper sleeve 9 are pulled again, and the sleeve 9 is placed above the treatment tube 5. At this time, the upper sleeve 9 can drive the positioning groove 13 on the internal second filter plate 12 to be stably inserted on the positioning rod 821. At the same time, by rotating the threaded rod 14 in the opposite direction, the thread is rotated into the threaded hole 822 on the positioning rod 821, and under the elastic action of the reset spring 15, the clamping rod 16 can be driven to automatically engage with the clamping groove 7 on the treatment tube 5 to complete the engagement installation. Then, the solenoid valve on the upper fixed tube 10 is opened, and deionized water is delivered to the treatment tube 5. After the delivery is completed, the solenoid valve can be closed.

[0041] At this time, under the driving action of the first servo motor 401, the turntable 402 can be driven to rotate stably, and then the limit plate 403 and the guide rod 404 can be driven to move at the same time. Under the movement of the guide rod 404, it can move into the guide groove 408 on the guide plate 407 and move the guide plate 407 to rotate. At the same time, the groove on the limit plate 403 is aligned with the guide plate 407, so it will not cause any obstruction to the rotating guide plate 407. Then the guide rod 404 moves out of the guide groove 408 on the guide plate 407. At this time, the limit plate 403 rotates to fit the guide plate 407 to prevent the guide plate 407 from shifting in position. This reciprocating process can drive the guide plate 407 to rotate intermittently, and each time it rotates 90°. The intermittent rotation of the guide plate 407 can drive the first diverter pipe 406 to move synchronously. Combined with the second diverter pipe 409 and the third diverter pipe 410, the processing cylinder 5 can be driven to perform automatic and stable intermittent flipping.

[0042] During the intermittent flipping of the processing tube 5, under the driving action of the second servo motor 801, the second gear 803 can be driven to rotate through the first gear 802 on the output shaft, and then the conveying tube 804 can be driven to rotate stably in the processing tube 5. At this time, under the rotation of the conveying tube 804, the push plate 807 can be driven to rotate synchronously, and then the support plates 818 on both sides can be pushed to move automatically to the side. During the movement of the support plate 818, the driven rod 816 can be driven to move inside the connecting tube 811, and then the connecting spring 814 can be squeezed through the connecting plate 815. Subsequently, under the continued rotation of the elliptical push plate 807, the pushing distance of the support plate 818 gradually becomes smaller. At this time, under the elastic action of the connecting spring 814, the driven rod 816 and the support plate 818 can be pushed to move and reset through the connecting plate 815. This reciprocating motion can drive the driven rod 816 and the support plate 818 to perform automatic and stable reciprocating motion.

[0043] At the same time, during the reciprocating motion of the driven rod 816, under the guidance of the sliding rod 813 and the sliding groove 817, the support plate 818 can be automatically reciprocated by the driven rod 816, and then the stirring rods 820 on each slider 819 can be automatically reciprocated and reciprocated. Combined with the reciprocating rotation of each scraper rod 809 and the overall intermittent flipping of the treatment tube 5, the crystallized product and the deionized water can be efficiently and evenly mixed, which effectively improves the washing efficiency and washing effect of the crystallized product. After the deionized water washing work is completed, the treatment tube 5 is flipped to a vertical state as a whole, and the waste water can be discharged through the fixed pipe 10; in summary, by controlling the solenoid valve on the fixed pipe 10, the diluted acid solution, the diluted alkali solution and ethanol can be transported in turn to perform multi-stage washing on the crystallized product. After the washing work is completed, the waste water can be discharged through the fixed pipe 10.

[0044] Then the staff can turn on the electric heating tube 24 in the insulation box 17 and the air pump 20 on the third air duct 18. Under the driving action of the air pump 20, air can be transported to the delivery tube 804 on the second air duct 805 through the insulation box 17, the third air duct 18 and the rubber hose 19, and the excess air in the treatment tube 5 is transported to the insulation box 17 again through the third diversion tube 410, the second diversion tube 409, the first diversion tube 406, the first air duct 405 and the rubber hose 19 in turn to complete the cycle. At this time, the air inside the treatment tube 5 circulates, and during the air circulation process, under the joint action of the filter frame 21, the dehumidification mesh plate 22, the activated carbon mesh plate 23 and the electric heating tube 24, the air can be filtered, dehumidified, purified and heated to avoid environmental pollution and heat loss. In addition, combined with the automatic flipping component 4 and the multi-functional stirring component 8, and with the dry hot air, the washed crystallized product can be comprehensively and efficiently dried, realizing the integrated processing of the crystallized product.

[0045] After the drying treatment, the treatment cylinder 5 is driven to a vertical state. At this time, the lower sleeve 9 is removed, and the treated crystallized product is placed in the lower sleeve 9 to facilitate its subsequent transportation. After the device is finished working, the magnetic cover frame 25 can be used to easily detach from the insulation box 17, and then the filter frame 21, dehumidification screen plate 22 and activated carbon screen plate 23 can be easily disassembled and assembled to ensure the convenience of subsequent cleaning and replacement.

[0046] The above embodiments are only used to illustrate the present invention, but not to limit the present invention. Although the present invention is described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention, and should be included in the scope of the claims of the present invention.

Claims

1. A titanium silicon molecular sieve catalyst, characterized in that: Prepared by the following steps: S1: Adding silicon source: Add deionized water into the reaction container, then drop the silicon source into the deionized water and stir slowly. After the dropwise addition is completed, continue stirring for 1 to 2 hours to fully hydrolyze the silicon source to form a uniform silicic acid solution; S2: Adding titanium source: Slowly adding titanium source to the silicate solution under vigorous stirring, at the same time, adding complexing agent to react with the titanium source, and continuing stirring for 1 to 2 hours to form a stable titanium complex; S3: preparing sol: slowly adding the template to the solution in S2, adding fatty acid and small molecule organic amine at the same time, and continuously stirring, then adding organosilane, sodium nitrate and lanthanum nitrate, and continuously stirring for 1 hour to form a uniform sol; S4: crystallization treatment: the sol in S3 is transferred to an autoclave for crystallization treatment, and a crystallized product with a regular crystal structure is gradually formed; S5: Post-treatment: After the crystallization treatment is completed, the reactor is opened, and the crystallized product is allowed to cool naturally to room temperature, and then the crystallized product is filtered, washed and dried through a processing device to remove excess templates and impurities, and a dry molecular sieve precursor is obtained; S6: Calcination treatment: The dried molecular sieve precursor is placed in a muffle furnace for calcination to remove the organic template and stabilize the crystal structure to form the final structure of the titanium silicon molecular sieve.

2. The preparation method according to claim 1, characterized in that: The silicon source in S1 is ethyl orthosilicate, the titanium source in S2 is tetrabutyl titanate, the complexing agent in S2 is acetylacetone, the template agent in S3 is tetrapropylammonium hydroxide, the fatty acid in S3 is stearic acid, the small molecule organic amine in S3 is triethanolamine, and the organic silane in S3 is trimethylsilane.

3. The preparation method according to claim 2, characterized in that: The molar ratio of tetraethyl orthosilicate: tetrabutyl titanate: tetrapropylammonium hydroxide: deionized water: fatty acid: acetylacetone: organic silane: sodium nitrate: lanthanum nitrate: small molecule organic amine is 1:0.1:0.1: 20：0.05：0.02：0.02：0.01：0.01：0.05。 4. The preparation method according to claim 3, characterized in that: The tetraethyl orthosilicate and tetrabutyl titanate in S2 undergo hydrolysis reaction in deionized water at a reaction temperature of 0°C to 30°C.

5. The preparation method according to claim 4, characterized in that: The hydrolysis reaction equation in S2 is: Si(OC2H5)4+4H2O→Si(OH)4+4C2H5OH. The generated silicic acid will further condense to form a silicon-oxygen tetrahedral structure.

6. The preparation method according to claim 1, characterized in that: The pH value of the mixed solution in S3 is 9~11.

7. The preparation method according to claim 1, characterized in that: The reactor in S4 is a stainless steel autoclave. The crystallization treatment in S4 is divided into pre-crystallization treatment and secondary crystallization treatment; pre-crystallization treatment: pre-crystallization is carried out at 100°C-150°C, and the pre-crystallization time is 0.5~8 hours; secondary crystallization treatment: hydrothermal crystallization is continued at 150°C-190°C for 4~96 hours.

8. The preparation method according to claim 1, characterized in that: The washing step in S5 uses deionized water, a diluted acid solution, a diluted alkali solution and ethanol to perform multi-stage washing on the crystallized product, wherein the diluted acid solution is diluted hydrochloric acid and the diluted alkali solution is diluted sodium hydroxide solution.

9. The preparation method according to claim 1, characterized in that: The calcination temperature of the muffle furnace in S6 is 550~600℃, the calcination time is 6~8 hours, and the heating rate is controlled at 1℃~2℃ / min.

10. The preparation method according to claim 1, characterized in that: The processing device used in S5 is a multifunctional processing device.

Images