CN112642467A - Selective disproportionation catalyst and preparation method and application thereof - Google Patents

Selective disproportionation catalyst and preparation method and application thereof Download PDF

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CN112642467A
CN112642467A CN201910953503.3A CN201910953503A CN112642467A CN 112642467 A CN112642467 A CN 112642467A CN 201910953503 A CN201910953503 A CN 201910953503A CN 112642467 A CN112642467 A CN 112642467A
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catalyst
gas
modifying
molecular sieve
modification
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CN112642467B (en
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李为
王月梅
孔德金
周亚新
龚燕芳
曹静
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a toluene selective disproportionation catalyst and application thereof, and mainly solves the problems of low activity of industrial catalysts and low selectivity of paraxylene products in the prior art. The invention relates to a selective disproportionation catalyst, which comprises a molecular sieve with the aperture of 0.50-0.62 nm, a binder and silicon dioxide, and modification elements comprising one or more of modification elements (1) Ag and/or Au, modification elements (2) Ga, Ge, Sn, Bi, Co and Ni, and modification elements (3) second main group elements. The catalyst with the composition can obtain a xylene product with high p-xylene content through toluene disproportionation reaction, and the problem is well solved. The invention adopts the shape-selective modification method of the catalyst to improve the performance of the catalyst, and can be applied in industry.

Description

Selective disproportionation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a selective disproportionation catalyst with high xylene product selectivity, a preparation method and application thereof.
Background
Para-xylene is a basic organic feedstock for large-scale production applications, primarily for the production of PTA. Toluene selective disproportionation is the most typical product selective reaction which converts toluene itself to a mixture of benzene and xylene, with the xylene product being a mixture of its three isomers and the most demanding para-xylene being over 90%. The common industrial catalyst adopts five-membered ring molecular sieve, especially ZSM-5 zeolite molecular sieve, which is a three-dimensional pore canal system formed by 10-membered oxygen rings and has an orifice and a pore diameter similar to the size of benzene molecules. The pore size characteristics of ZSM-5 zeolite allow for rapid diffusion of para-xylene with a molecular diameter of 0.63 nm, while diffusion of ortho-xylene and meta-xylene with a molecular diameter of 0.69 nm is more limited. In a toluene disproportionation reaction system, the diffusion rate of each species in ZSM-5 pore channels is related as follows: benzene is more than toluene, more than p-xylene, more than m-xylene and more than o-xylene, and the content of p-xylene isomers in xylene products which is far higher than thermodynamic equilibrium concentration can be obtained by adopting a molecular sieve. The final product is still of equilibrium composition because the acid sites on the outer surface of the molecular sieve do not selectively isomerize to the para-rich product diffusing out of the channels. Therefore, to obtain a catalyst with higher para-selectivity, the ZSM-5 molecular sieve must be modified. In the molecular sieve, because the joint of the two pore canals is larger and a larger space exists at the joint, paraxylene can be immediately isomerized into a xylene isomer at the position where the paraxylene diffuses, and a part of paraxylene can be converted into ethylbenzene, thereby causing larger influence on selective disproportionation. However, after modification, because of partial blockage of the modified pore opening, the diffusion efficiency is greatly reduced, and partial active centers are lost, so that the conversion rate of toluene is greatly reduced, namely the reaction conversion rate and the 'reverse effect' of selectivity.
In the method for preparing the toluene shape-selective disproportionation catalyst by only modifying organosilicon in documents US5367099A, US5607888A and WO9746636a1, macromolecular compounds with thermal decomposition property are selected and deposited on the outer surface of the molecular sieve by a certain method, and then the macromolecular compounds are thermally decomposed by high-temperature treatment and converted into an inert coating, so that the acid centers on the outer surface of the molecular sieve are shielded, the size of the openings is reduced to a certain extent, and the openings are blocked. Although the performance of the catalyst prepared by the method has higher selectivity to the dimethylbenzene, the preparation method adopts the organic silicon, and the processes of loading, dipping, roasting and the like are complicated, so that the dealumination of a molecular sieve framework is caused, the diffusion efficiency is obviously reduced, the non-aromatic hydrocarbon byproducts generated by the selective disproportionation reaction of the methylbenzene are increased, the conversion rate of the methylbenzene is reduced more, and the yield of the dimethylbenzene is reduced.
In the united states patent US6486373B1, a composite molecular sieve method is adopted to improve the activity of the toluene disproportionation catalyst, and boron is introduced into the framework of the molecular sieve. A ZSM-5 molecular sieve is used as a matrix, a combination body with other pore channel structures is formed on the surface of the ZSM-5 molecular sieve, and then the ZSM-5 molecular sieve is formed and subsequently modified to improve the reaction activity. However, as boron is in the framework, part of boron is not easy to enter the framework and is left in the pore channel, the obstruction of the reactant in the pore channel of the ZSM-5 molecular sieve is increased, the residence time of toluene is increased, side reactions are increased, and the conversion rate of toluene is lower.
The ZSM-5 molecular sieve with the shell structure of the all-silica zeolite or the high-silica zeolite is adopted in CN101722033A, CN102671694A and CN103539152A, although the selective reaction is realized, the shell layer is difficult to cover the surface of the all-silica zeolite for the catalyst, and meanwhile, the shell structure in the synthesis of the core-shell structure is fragile and difficult to carry out post-treatment, so that the activity and the selectivity of the catalyst are low, and the industrial application is hindered.
The Ag modified toluene disproportionation and transalkylation catalyst has the reaction promoting effect. In CN1287884A and Japanese patent No. 49-46295, mordenite is used as the active center of the molecular sieve, Ag can enter the pore channels of the molecular sieve because the pore channels of the molecular sieve such as the mordenite with twelve-membered rings are larger, and the activity of the catalyst is improved by modifying metals including Ag elements. However, the twelve-membered ring molecular sieve is not suitable for the toluene shape selective disproportionation reaction process, and if the Ag modified ZSM-5 is adopted, the acid center of the Ag modified ZSM-5 molecular sieve is not easy to adopt due to the small pore channel of the molecular sieve.
Disclosure of Invention
The invention aims to solve the problems of lower conversion rate of toluene modified by silicon dioxide and lower selectivity of p-xylene products in the prior art. The invention adopts the modification element and the molecular sieve to combine and modify to form the monolithic catalyst, so that the selectivity of the p-xylene in the reaction product of the toluene selective disproportionation reaction on the catalyst is improved, the reaction activity of the catalyst is also improved, and the problem is better solved.
One purpose of the invention is to provide a selective disproportionation catalyst, which comprises a molecular sieve, a modifying element, a binder and silica, wherein the modifying element comprises a modifying element (1), a modifying element (2) and a modifying element (3), and the components are calculated by weight:
Figure BDA0002226501110000031
the weight parts of the components are based on the total weight of the components.
Wherein the content of the first and second substances,
the modifying element (1) is Ag and/or Au;
the modified element (2) is one or more of Ga, Ge, Sn, Bi, Co and Ni;
the modifying element (3) is one or more of second main group elements;
the aperture of the molecular sieve is 0.50-0.62 nm; the silicon-aluminum molecular ratio of the molecular sieve is 12-100, and preferably 20-70.
The catalyst with the structure is adopted, and the toluene disproportionation reaction is carried out to obtain the xylene product with high p-xylene yield.
For the technical scheme provided above:
because the molecular sieve matrix required by the toluene selective disproportionation reaction has higher activity requirement, the molecular sieve with more suitable acidity and suitable pore channels adopted by the common industrial catalyst is taken as an activity base, wherein the molecular sieve with the suitable pore channels is at least one of the molecular sieves with the following structures: MFI (e.g., ZSM-5 molecular sieve (0.53 nm-0.56 nm, 0.51 nm-0.55 nm) three-dimensional pore channels), MEL (e.g., ZSM-11 molecular sieve (0.53 nm-0.54 nm)), MTW (e.g., ZSM-12 molecular sieve (0.57-0.60 nm)), TON (e.g., NU-10, ZSM-22 molecular sieve (0.45 nm-0.55 nm), Theta-1(0.46 nm-0.57 nm)).
The invention preferably adopts one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-22, NU-10 and Theta-1 molecular sieves. The invention particularly teaches the use of ZSM-5 molecular sieves with a silica to alumina ratio (SiO)2/Al2O3Molecular ratio) of 12 to 100. The lower the silica-alumina ratio of the molecular sieve framework, the more the disproportionation active center is, but the synthesis of the molecular sieve with too low molecular sieve is difficult, the crystallization rate of the molecular sieve is lower, and the molecular sieve is not suitable for modification. Therefore, the preferred Si/Al ratio of the ZSM-5 molecular sieve and other molecular sieves is 20-70.
The second main group element is one or more of Be, Mg, Ca, Sr and Ba, preferably one or two of Mg and Ca.
The binder is an inert binder, preferably at least one of silicon dioxide, aluminum oxide and clay. The binder is used as a forming binder of the molecular sieve.
The invention also aims to provide a preparation method of the selective disproportionation catalyst, which comprises the following steps: and forming the molecular sieve and a binder, modifying the modifying element and the silicon dioxide, and roasting to obtain the selective disproportionation catalyst, wherein the molecular sieve is modified or not by the modifying element.
Preferably, the preparation method comprises the steps of:
mixing the molecular sieve with a binder, and roasting and forming to obtain a catalyst modified precursor;
wherein the silica modification comprises silica modification of the catalyst modification precursor with a silica modifier;
wherein the modifying element modification comprises at least one of the following steps: 1) modifying the modifying element in the process of preparing the molecular sieve, preferably comprising at least one condition of the modification in the synthesis process of the molecular sieve, the Na exchange process of the molecular sieve or the Na exchange of the molecular sieve; 2) modifying with a modifying element during the shaping of the catalyst modified precursor, and 3) modifying with a modifying element after the shaping of the catalyst modified precursor, including at least one of modifying with a modifying element before the modifying with silica of the catalyst modified precursor, modifying with a modifying element during the modifying with silica of the catalyst modified precursor, and modifying with a modifying element after the modifying with silica of the catalyst modified precursor.
Modifying the modifying element, and if the step 3) is adopted, roasting the catalyst modified precursor after the modifying element is introduced; in the same process, all the modifying elements in the process can be introduced together according to actual conditions, and then the catalyst modifying precursor is calcined at one time, or the modifying elements can be introduced in the same step in batches, and the catalyst modifying precursor is calcined between the introduction of two adjacent batches of the modifying elements or only the catalyst modifying precursor is dried (dried). If the introduction of the modifying element is carried out before or after the modification of the catalyst modified precursor by the silica, the modification of the modifying element and the modification of the silica can be carried out in the next step after the calcination, or the modification of the catalyst modified precursor can be carried out only after the drying (baking), as long as the final step of the preparation method of the catalyst of the present invention is the calcination.
Wherein the Ag and/or Au element modification mode comprises introducing element sources through one or more modes of impregnation, ion exchange or mixed addition in the catalyst modification precursor forming process. The Ag source is at least one of a silver compound solution, a silver salt complex solution and a water-soluble Ag complex solution, and preferably at least one of silver nitrate, silver fluoride, silver perchlorate, silver chlorate, an amino complex Ag ion solution, a cyano complex Ag ion solution and a thiosulfate complex Ag ion solution. The Au source is at least one of gold trichloride and aqua regia diluted solution.
The second main group element modification mode comprises introducing the second main group element by one or more modes of element source impregnation, ion exchange or mixed addition in the catalyst modification precursor forming process. The second main group element source is at least one of nitrate, sulfate and halide solution of the second main group element which is soluble in water.
The Ga, Ge, Sn, Ni, Co and Bi modification mode comprises introducing Ga, Ge, Sn, Ni, Co and Bi elements by one or more modes of element source impregnation, vapor deposition modification, ion exchange or mixed addition in the catalyst modification precursor forming process. Wherein the Ga source is at least one of solutions of gallium nitrate, gallium sulfate, gallium halide and gallium ammonium sulfate; the Ge source is at least one of nitrate, halide and sulfate of germanium; the Sn source is at least one of nitrate, halide and sulfate of tin; the Bi source is at least one of nitrate, halide and sulfate of bismuth; the Ni source is at least one of nitrate, halide and sulfate of nickel; the Co source is at least one of nitrate, halide and sulfate of cobalt.
In the selective disproportionation catalyst of the present invention, the silica is obtained by modifying a molecular sieve with a silica modifier and calcining the modified molecular sieve on the surface of a molecular sieve grain.
The modification mode of the silicon dioxide comprises introducing the silicon dioxide modifier through one or more modes of impregnation and loading.
The silicon dioxide modifier is at least one of silicone oil, silane, silicone resin, siloxane and polysiloxane, preferably at least one of silicone oil, methyl silicone oil and phenyl trimethoxy silane.
The catalyst is prepared according to the technical scheme, and a silicon dioxide modified molecular sieve catalyst is adopted. Through modification of silicon dioxide, the acid center and the pore opening on the surface of the molecular sieve are shrunk, so that the diffusion of m-xylene and o-xylene is limited, and p-xylene is preferentially diffused. The silicon dioxide is arranged on the surface of the molecular sieve crystal grain, and the content of the modified silicon dioxide is 1-20 parts.
The catalyst prepared according to the technical scheme adopts the silver and gold element modified molecular sieve catalyst, and can be loaded or ion-exchanged on the surfaces of molecular sieve particles. As the ion radius of Ag and Au is larger, the Ag and Au ions are generally loaded on the acid center of the surface of the molecular sieve and can partially cover the surface of the catalyst, thereby improving the modification efficiency of the surface of the molecular sieve. Ag. After Au is combined with the molecular sieve, Au can stay on the surface of the molecular sieve in the subsequent heating and other treatment processes to modify the acidity of the orifice and the pore channel of the molecular sieve.
According to the technical scheme, one or more of Ga, Ge, Sn, Ni, Co and Bi are introduced during preparation of a molecular sieve, ion exchange, vapor deposition, impregnation or kneading molding. By adding Ge, Ni, Co, Bi or Sn, the generation of p-xylene is effectively improved. The addition of Ga inhibits the side reaction of converting toluene into ethylbenzene, thereby improving the selectivity of xylene products in the converted toluene.
According to the technical scheme for preparing the catalyst, the second main group element is preferably one or more of Be, Mg, Ca, Sr and Ba, and more preferably one or two of Mg and Ca. As Ge, Sn, Ag, Au and other metals or oxides thereof have larger diameters, the PX para-position selectivity is effectively increased by adding the second main group.
According to the technical scheme, in the preparation method of the toluene selective disproportionation catalyst, silicon dioxide is introduced from silicone oil, silane, silicone resin, siloxane or polysiloxane. And after the modification by the silica modifier, roasting to obtain the catalyst.
More preferably, the preparation method of the selective disproportionation catalyst comprises the steps of mixing the molecular sieve with a binder, roasting, molding, impregnating in a modified element source, drying and roasting; then impregnating the catalyst in a silica modifier, and roasting to obtain the selective disproportionation catalyst.
Wherein, the silver source solution is obtained by directly dissolving a silver compound in water. The silver source impregnation method adopts equal-volume impregnation or ion exchange impregnation and the like.
When equal-volume impregnation is adopted, the concentration of the silver compound in the silver source solution is calculated according to the required Ag loading capacity; when impregnation is performed by ion exchange, the silver compound in the silver source solution is preferably present at a concentration of less than 2%.
According to the technical scheme, the second main group element modification mode comprises introducing the second main group element by one or more modes of element source impregnation, ion exchange or catalyst modification precursor forming.
According to the technical scheme, the Ga, Ge, Sn, Ni, Co and Bi modification mode comprises introducing Ga, Ge, Sn, Ni, Co and Bi elements in one or more modes of element source impregnation, vapor deposition modification, ion exchange or mixing and adding in the catalyst modification precursor forming process.
In the solution of the present invention, if the Ag, Au, Ga, Ge, Sn, Ni, Co, Bi and the source of the second main group element are introduced into the catalyst precursor by molding, the salt may be dissolved and then directly added to the kneaded mixture.
When the Ag, Au, Ga, Ge, Sn, Ni, Co, Bi and the second main group element source are impregnated, the impregnation temperature is preferably constant at the normal temperature to 100 ℃ for 1 to 30 hours, and more preferably constant at the normal temperature to 60 ℃ for 1 to 20 hours.
In the vapor deposition modification treatment of Ga, Ge, Sn, Ni, Co and Bi, the treatment is preferably carried out at the temperature of normal temperature to 600 ℃ for 0.5 to 20 hours in an inert atmosphere, and more preferably at the temperature of 100 to 500 ℃ for 1 to 6 hours.
If Ag, Au, Ga, Ge, Sn, Ni, Co, Bi and the second main group element source are introduced in the synthesis process of the molecular sieve, solution exchange is directly adopted after the sodium exchange of the molecular sieve. The sodium-free synthesized molecular sieve is added with Ag, Au, Ga, Ge, Sn, Ni, Co and Bi sources in the synthesis process, and the second main group element source is introduced by an ion exchange method after the synthesis.
When the silica modification is performed first, the catalyst needs to be soaked in an organic solvent because the catalyst modified by the silica has strong hydrophobicity. In the subsequent impregnation of the second main group element source with the same volume of Ag, Au, Ga, Ge, Sn, Ni, Co, Bi, or the like or by other methods, a water-soluble organic substance such as ethanol is added to the impregnation solution to uniformly impregnate the silica-modified catalyst.
The impregnation method of the silicon dioxide modifier is preferably an ion exchange method, and during ion exchange, the impregnation temperature is preferably constant at the normal temperature to 99 ℃ for 1 to 60 hours, and more preferably constant at the normal temperature to 90 ℃ for 2 to 10 hours.
In the preparation method of the catalyst, in the drying and roasting processes, the drying temperature is preferably normal temperature to 120 ℃, more preferably 30 to 120 ℃, and the drying time is preferably more than 3 hours, more preferably 4 to 24 hours. The roasting is carried out in air or inert gas-containing atmosphere, and the roasting temperature is 300-800 ℃, preferably 450-800 ℃, and more preferably 450-600 ℃; the roasting time is 0.1-20 hours, preferably 2-20 hours, and more preferably 2-5 hours.
According to the technical scheme of the preparation method of the toluene selective disproportionation catalyst, modification elements such as Ag, Au, Ga, Ge, Sn, Ni, Co, Bi and the like on the surface of the molecular sieve are firstly carried out, and then selective modification of silicon dioxide is carried out. The yield of xylene can also be improved by modifying silica with a modifying element and then modifying silica with a modifying element, but this method is not as high as the above method.
In the actual preparation, the Ag and Au modified molecular sieve catalyst is directly used for evaluation test, the toluene conversion rate is reduced, the characteristic of accelerating disproportionation reaction in mordenite modification is not shown, and the toluene conversion rate is reduced.
The method of the invention combines Ag, Au, Ga, Ge, Sn, Ni, Co and Bi with silicon dioxide for modification, the conversion rate of toluene is obviously increased, and the yield of p-xylene is improved. The yield of the p-xylene can be further improved by further adopting the second main group for modification.
The invention also aims to provide the application of the selective disproportionation catalyst with high xylene conversion in the selective disproportionation reaction of toluene.
In the selective disproportionation reaction of toluene, the reaction is preferably carried out at a reaction temperature of 300-500 ℃, a pressure of 0.1-10 MPa, a hydrogen-hydrocarbon ratio of 0-10 and a weight space velocity of 0.1-10 h-1Under the condition of the reaction.
In the technical scheme, the toluene selective disproportionation catalyst and the preparation method thereof. The catalyst is prepared by adopting a novel mode of combining Ag, Au, Ga, Ge, Sn, Ni, Co and Bi modification with silica modification, and the catalyst with better performance is obtained by the catalyst preparation method which improves the conversion rate of toluene and has higher selectivity of xylene products. The ionic radius of Ag, Au, Ge, Sn, Ni, Co and Bi is larger, and the ionic radius is combined with the ammonium type or ammonium type position on the surface of the molecular sieve, so that the acidic center position of strong acid on the surface of the molecular sieve is passivated, and the modification difficulty of silicon dioxide is reduced. The method for modifying overcomes the problems that the silicon dioxide is inert, the combination of the silicon dioxide and the surface of the molecular sieve crystal grain surface acid center is influenced, the passivation can be realized only by high roasting, and the selective modification cannot be realized. In the traditional molecular sieve catalyst for shape selective disproportionation of toluene, in order to achieve higher selectivity, the surface of more silicon dioxide is passivated, the diffusion is severely limited, and the toluene conversion activity is lower. Therefore, the modification method overcomes the defects that the prior modification steps are more, the structure formed by external force covers the surface of the molecular sieve to form a structure with a molecular size separation function, and simultaneously, the molecular diffusion efficiency is greatly increased, so that the catalyst has higher toluene conversion rate and PX selectivity, the retention time of aromatic hydrocarbon in an active molecular sieve is reduced, the cracking probability of the aromatic hydrocarbon is reduced, and the toluene conversion rate and the p-xylene selectivity are higher.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The method for determining the catalyst composition comprises the following steps:
the weight content of the molecular sieve and the binder are calculated by the adding amount of raw materials during molding, and the weight content of the molecular sieve and the binder are calculated by adding the amount of a metal source when Ag, Au, Ga, Ge, Sn, Ni, Co, Bi and the second main group element are dipped in the same volume. Wherein the salts of the metal source are commercially available.
Ag. Au, Ga, Ge, Sn, Ni, Co, Bi, and a second main group element: obtained by ICP (inductively coupled plasma) analysis. The ICP test conditions were: the Varian 700-ES series XPS instrument.
Final silica loading of catalyst modified with silica: calculated from the weight difference before and after modification. The weight of the catalyst before modification is weighed, the catalyst obtained after modification roasting is weighed, and the difference between the two is compared to obtain the modified weight ratio. Characterization can also be performed using XRF (X-ray fluorescence) or ICP methods. The weight of the total alumina is not changed in the modification process, and the content of the modified silica is calculated by representing the change of the obtained silicon-aluminum ratio. XRF test conditions were: rigaku ZSX 100e model XRF instrument.
The determination method of the composition of the reaction product comprises the following steps:
in the present invention, the reactant stream composition is determined by gas chromatography. The chromatography model is Agilent 7890A, a FID detector is arranged, the FFAP capillary chromatographic column is used for separation, the temperature of the chromatographic column is programmed to be 90 ℃ initially, the temperature is kept for 15 minutes, then the temperature is raised to 220 ℃ at the speed of 15 ℃/minute, and the temperature is kept for 45 minutes.
Calculation of the data of the main results of the examples and comparative examples:
toluene conversion (weight of toluene entering reactor-weight of toluene at reactor outlet)/(weight of toluene entering reactor) 100%;
para-xylene selectivity (mass percent of para-xylene in the reaction product)/(mass percent of xylene in the reaction product) 100%;
p-xylene product selectivity (mass of p-xylene produced by the reaction)/(mass of toluene reacted) 100.
[ example 1 ]
Mixing a ZSM-5 molecular sieve (provided by Zhongpetrochemical catalyst company and the same below) with a silicon-aluminum molecular ratio of 25 and a binder silicon dioxide (from 40 percent of commercial sodium-free silica sol and the same below), molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 79 weight percent of the ZSM-5 molecular sieve and 21 weight percent of the binder; taking 100.0g of the catalyst precursor, and taking AgNO3And Mg (NO)3)2Solution (containing AgNO)35.0% by weight of Mg (NO)3)2Weight concentration of 1.5%) 60.0g of the mixture is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃, and continuously taken SnSO4Solution (containing SnSO)410.0% by weight) 60.0g of the mixture was immersed at room temperature for 2 hours in an equal volume, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. The catalyst obtained above was further modified by dipping 40.0g of Dow Corning 550 silicone oil (30 wt% (hereinafter, the same), solvent n-hexane, silicone all commercially available, hereinafter, the same) in an equal volume at 60 ℃ for 5 hours, holding the temperature at 150 ℃ for 10 hours, and calcining at 600 ℃ for 5 hours (calcining in air, hereinafter, the same). And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the hydrogen-hydrocarbon molar ratio is 1.5, the conversion rate of toluene is 39.3 percent, the para-xylene selectivity is 90.1 percent, and the para-xylene product selectivity is 48.0 percent.
[ example 2 ]
The molecular ratio of silicon to aluminum is 14Mixing the ZSM-5 molecular sieve and the adhesive silicon dioxide, molding, drying, and roasting at 500 ℃ (for 6 hours) to obtain a catalyst modified precursor containing 63 wt% of the ZSM-5 molecular sieve and 37 wt% of the adhesive; taking 100.0g of the catalyst precursor, and taking AgNO3And Ca (NO)3)2Solution (containing AgNO)33.9% by weight, Ca (NO)3)2Weight concentration of 1.0%) 60.0g of the mixture is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃, and continuously taken SnSO460.0g of the solution (with weight concentration of 6.0 percent) is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃ and then roasted for 3 hours at 550 ℃. The prepared catalyst is continuously modified, 45.0g of Dow Corning 710 silicone oil (the weight concentration is 40 percent, the solvent No. 90 does not contain aromatic hydrocarbon solvent) is adopted to be dipped for 9 hours at the equal volume under the temperature of 90 ℃, the constant temperature of 120 ℃ is kept for 10 hours, and the catalyst is roasted for 5 hours under the temperature of 600 ℃. And repeating the modification of the silicone oil for 3 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. (all the examples below were evaluated by this method). At a weight space velocity of 8.0h－1Under the conditions that the reaction temperature is 400 ℃, the reaction pressure is 5.0MPa and the hydrogen-hydrocarbon molar ratio is 4, the conversion rate of toluene is 33.6 percent, the para-xylene selectivity is 89.1 percent, and the para-xylene product selectivity is 48.0 percent.
[ example 3 ]
Mixing a ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 99.3, a binder silica and alumina (from pseudoboehmite, sold in the market), molding, drying, roasting at 600 ℃ (constant temperature for 2 hours) to obtain a catalyst modified precursor containing 80 wt% of the ZSM-5 molecular sieve, 10 wt% of the silica and 10 wt% of the alumina; taking 100.0g of the catalyst precursor, and taking AgClO3Solution and Ba (NO)3)2Solution (containing AgClO)3Concentration by weight 2%, Ba (NO)3)20.5%) 60.0g of the above-mentioned raw materials were immersed in the same volume at room temperature for 2 hours, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. Continue to take GeCl460.0g of the solution (with weight concentration of 6.0 percent) is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃ and then roasted for 3 hours at 550 ℃. The above-mentioned system isThe obtained catalyst is continuously modified, 45.0g of Dow Corning 710 silicone oil (with the weight concentration of 30 percent and solvent No. 90 without aromatic solvent) is dipped for 9 hours at the equal volume under the temperature of 90 ℃, the constant temperature of 120 ℃ is kept for 10 hours, and the baking is carried out for 5 hours under the temperature of 600 ℃. And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 10.0h－1Under the conditions that the reaction temperature is 500 ℃ and the reaction pressure is 10.0MPa, the conversion rate of toluene is 29.0 percent, the para-selectivity of p-xylene is 91.1 percent, and the selectivity of p-xylene products is 49.5 percent.
[ example 4 ]
Mixing a ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 90.0 and a binder silicon dioxide, forming, drying, and roasting at 530 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 92 wt% of the ZSM-5 molecular sieve and 8 wt% of the silicon dioxide; taking 100.0g of the catalyst precursor, and taking AgClO3And Sn (NO)3)2Solution (containing AgClO)36% by weight of Sn (NO)3)2Soaking 60.0g of 2.0% by weight in the same volume at room temperature for 2 hr, oven drying at 120 deg.C for 6 hr, and continuously collecting Sr (NO)3)260.0g of the solution (with the weight concentration of 1.0 percent) is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃ and then roasted for 3 hours at 550 ℃. Continuously modifying the prepared catalyst, adopting 10.0g (without solvent) of phenyltrimethoxysilane to perform isovolumetric immersion for 2 hours at normal temperature, roasting for 3 hours at 550 ℃, and repeating the modification of silicon dioxide for 1 time to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 0.1h－1Under the conditions that the reaction temperature is 300 ℃ and the reaction pressure is 10.0MPa, the conversion rate of toluene is 32.6 percent, the para-xylene selectivity is 92.1 percent, and the para-xylene product selectivity is 49.8 percent.
[ example 5 ]
Mixing a ZSM-11 molecular sieve with a silicon-aluminum molecular ratio of 25 and a binder silicon dioxide, molding and drying,Roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 75 wt% of ZSM-11 molecular sieve and 25 wt% of silicon dioxide; taking 100.0g of the catalyst precursor, and taking AuCl3Solution and Sn (NO)3)2Solution (containing AuCl)30.1% by weight of Sn (NO)3)2Weight concentration of 6.0%) 60.0g, soaking at room temperature for 2 hr, oven drying at 120 deg.C for 6 hr, and collecting Ba (NO)3)260.0g of the solution (with weight concentration of 1.0%) is immersed for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃ and then roasted for 3 hours at 550 ℃. 45.0g of Dow Corning 710 silicone oil (toluene is used as a solvent, and the mass content is 20 percent) is dipped for 9 hours at the equal volume at the temperature of 90 ℃, is kept at the constant temperature of 120 ℃ for 10 hours, and is roasted for 5 hours at the temperature of 600 ℃. And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 6.0h－1Under the conditions that the reaction temperature is 420 ℃, the reaction pressure is 2.0MPa and the hydrogen-hydrocarbon molar ratio is 1.0, the conversion rate of toluene is 35.2 percent, the para-xylene selectivity is 88.0 percent, and the para-xylene product selectivity is 45.6 percent.
[ example 6 ]
Mixing a ZSM-22 molecular sieve with a silicon-aluminum molecular ratio of 30 and a binder silicon dioxide, molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 65 wt% of the ZSM-22 molecular sieve and 35 wt% of the silicon dioxide; taking 100.0g of the catalyst precursor, and taking AgF solution and Ba (NO)3)2Solution (containing 5.0% by weight of AgF, Ba (NO)3)2Weight concentration 6.0%) 60.0g of the above-mentioned raw materials are immersed for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 deg.C and roasted for 3 hours at 550 deg.C. GeCl for preparing the catalyst in nitrogen atmosphere4Continuing vapor deposition modification, and then roasting at 500 ℃ for 2 hours to obtain the deposited GeO2The amount was 2.0 g. 42.0g (30% by weight) of methyl silicone oil (1000cps) is dipped in the solution at 60 ℃ for 5 hours with equal volume, the temperature is kept at 120 ℃ for 10 hours, and the solution is roasted at 600 ℃ for 5 hours. And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 2.0h－1The reaction temperature is 420 ℃, the reaction pressure is 0.6MPa, and the hydrogen-hydrocarbon molar ratio is 0.5, the toluene conversion rate is 38.2%, the para-xylene selectivity is 88.0%, and the para-xylene product selectivity is 47.6%.
[ example 7 ]
Mixing a ZSM-12 molecular sieve with a silicon-aluminum molecular ratio of 40 and a binder silicon dioxide, molding, drying, and roasting at 650 ℃ (constant temperature for 2 hours) to obtain a catalyst modified precursor containing 75 wt% of the ZSM-12 molecular sieve and 25 wt% of the silicon dioxide; taking 100.0g of the catalyst precursor, and taking AgNO3And Sn (NO)3)2Solution (containing AgNO)32.1% by weight of Sn (NO)3)2Weight concentration 1.0%) 62.0g of the above-mentioned raw materials were immersed in the same volume at room temperature for 2 hours, dried at 120 ℃ for 6 hours, and calcined at 550 ℃ for 3 hours. Taking Mg (NO)3)2Solution of (containing Mg (NO)3)2Weight concentration 0.5%) 62.0g of the above-mentioned materials were immersed in the same volume at room temperature for 2 hours, and then dried at 120 ℃ for 6 hours. Continuously modifying the prepared catalyst, soaking 45.0g of Dow Corning 710 silicone oil at 90 ℃ for 9 hours in equal volume, keeping the temperature at 120 ℃ for 10 hours, roasting at 600 ℃ for 5 hours, and modifying the silicone oil to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the activity and selectivity of the toluene disproportionation reaction were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 5.0h－1The reaction temperature is 410 ℃, the reaction pressure is 0.1MPa, and the hydrogen-hydrocarbon molar ratio is 1.8, the toluene conversion rate is 37.8%, the para-xylene selectivity is 85.1%, and the para-xylene product selectivity is 45.6%.
[ examples 8 to 11 ]
Mixing a ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 30 and a binder silicon dioxide, molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 80 wt% of the ZSM-5 molecular sieve and 20 wt% of the silicon dioxide; taking 100.0g of the catalyst precursor, taking 60.0g of nitrate solution of the modified element 1 and nitrate solution of the modified element 2 (the weight ratio of the modified element 1 to the catalyst and the weight content of the modified element 2 are shown in the table 1), soaking for 2 hours at normal temperature in the same volume, drying for 6 hours at 120 ℃, and roasting for 3 hours at 550 ℃. Taking a solution of nitrate of a modifying element 3 (the weight ratio of the nitrate to the catalyst and the weight content of the modifying agent 3 are shown in table 1), soaking for 2 hours at normal temperature in an equal volume, and drying for 6 hours at 120 ℃. The catalyst is modified continuously, 40.0g of Dow Corning 550 silicone oil (with weight concentration of 30 percent and solvent of n-hexane) is dipped for 3 hours at the temperature of 90 ℃ in equal volume, the temperature is kept constant for 10 hours at the temperature of 150 ℃, and the catalyst is roasted for 3 hours at the temperature of 600 ℃. The prepared catalyst is continuously modified, and the silicone oil modification is repeated for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount of each of the above examples was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus. At a weight space velocity of 3.0h－1The results of the evaluation were shown in Table 2, wherein the reaction temperature was 445 ℃, the hydrogen-hydrocarbon molar ratio was 2.2, and the reaction pressure was 2.0 MPa.
[ example 12 ]
A sodium ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 25 (the molecular sieve is provided by China petrochemical catalyst company), performing exchange for 3 times at 90 ℃ by using an ammonium nitrate aqueous solution with a concentration of 10% and a solid-to-liquid ratio of 1:8, performing exchange filtration by using a silver nitrate aqueous solution (a silver nitrate ammonia complex with a concentration of 0.2%, magnesium nitrate with a concentration of 0.2% and a solid-to-liquid ratio of 1:4) containing magnesium nitrate and silver nitrate, drying at 150 ℃ to obtain the molecular sieve, mixing, molding and drying the prepared ZSM-5 molecular sieve and a binder silicon dioxide (from 40% commercially available sodium-free silica sol, the same applies below) and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 79 wt% of the molecular sieve and 21 wt% of the binder; taking 100.0g of the catalyst precursor, and taking AgNO3And Mg (NO)3)2Solution (containing AgNO)3Concentration by weight 4.0%, Mg (NO)3)2Weight concentration of 1.0%) 60.0g of the mixture is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃, and continuously taken SnSO4Solution (containing)SnSO48.0% by weight) 60.0g of the mixture was immersed at room temperature for 2 hours in an equal volume, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. The catalyst obtained above was further modified by dipping 40.0g of Dow Corning 550 silicone oil (30 wt% (hereinafter, the same), solvent n-hexane, silicone all commercially available, hereinafter, the same) in an equal volume at 60 ℃ for 5 hours, holding the temperature at 150 ℃ for 10 hours, and calcining at 600 ℃ for 5 hours (calcining in air, hereinafter, the same). And repeating the modification of the silicone oil for 1 time to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the hydrogen-hydrocarbon molar ratio is 1.0, the conversion rate of toluene is 39.0 percent, the para-xylene selectivity is 87.1 percent, and the para-xylene product selectivity is 47.3 percent.
[ example 13 ]
Mixing a ZSM-5 molecular sieve (provided by Zhongpetrochemical catalyst company and the same below) with a silicon-aluminum molecular ratio of 40 and a binder silicon dioxide (from 40 percent of commercial sodium-free silica sol and the same below), molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 79 weight percent of the ZSM-5 molecular sieve and 21 weight percent of the binder; taking 100.0g of the catalyst precursor, and taking Ag (NH)3)2Cl and Mg (NO)3)2Solution (containing Ag (NH)3)2Cl concentration 3.0 wt%, Mg (NO)3)260.0g of 1.5 percent by weight, soaking for 2 hours at normal temperature in the same volume, drying for 6 hours at 120 ℃, and continuously taking Ga (NO)3)2Solution (containing Ga (NO)3)25.0% by weight) 60.0g of the mixture was immersed at room temperature for 2 hours in an equal volume, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. The catalyst is further modified by soaking 40.0g of Dow Corning 710 silicone oil (with weight concentration of 24% (the same below) and solvent n-hexane) in the same volume at 60 deg.C for 5 hr, keeping the temperature at 150 deg.C for 10 hr, and calcining at 550 deg.C for 5 hr (in air, the same below). And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the hydrogen-hydrocarbon molar ratio is 0.7, the conversion rate of toluene is 39.0 percent, the para-xylene selectivity is 89.1 percent, and the para-xylene product selectivity is 48.1 percent.
[ COMPARATIVE EXAMPLE 1 ]
Mixing a ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 25 and a binder silicon dioxide, molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 79 wt% of the ZSM-5 molecular sieve and 21 wt% of the silicon dioxide; 100.0g of the catalyst precursor is taken, 40.0g of Dow Corning 550 silicone oil (with the weight concentration of 30 percent and the solvent of n-hexane) is adopted to be soaked for 5 hours at the temperature of 60 ℃ in equal volume, the temperature is kept constant for 10 hours at the temperature of 150 ℃, and the catalyst precursor is roasted for 5 hours at the temperature of 600 ℃. And repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the molar ratio of hydrogen to hydrocarbon is 1.5, the conversion rate of toluene is 31.0 percent, the para-xylene selectivity is 82.1 percent and the para-xylene product selectivity is 41.5 percent.
[ COMPARATIVE EXAMPLE 2 ]
Mixing a ZSM-5 molecular sieve with a silicon-aluminum molecular ratio of 25 and a binder silicon dioxide, molding, drying, and roasting at 550 ℃ to obtain a catalyst A containing 79 wt% of the ZSM-5 molecular sieve and 21 wt% of the silicon dioxide; taking 50.0g of the catalyst A and AgNO3Solution (containing AgNO)3Weight concentration of 17%) 30.0g of the above-mentioned material was immersed in an equal volume at room temperature for 2 hours, dried at 120 ℃ for 6 hours, and calcined at 550 ℃ for 3 hours. Catalyst B was prepared as described above. The catalyst composition is shown in table 1.
Taking 15.0 g of each of the catalysts A and B, carrying out the investigation of the activity and selectivity of the toluene disproportionation reaction on a fixed bed reaction evaluation device(all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1The reaction temperature is 430 ℃, the reaction pressure is 2.8MPa, and the hydrogen-hydrocarbon molar ratio is 1.5, so that the catalyst A: the conversion rate of toluene is 48.9%, the para-selectivity of p-xylene is 23.9%, and the selectivity of p-xylene product is 12.5%. Reaction results catalyst B: the conversion rate of toluene is 44.0 percent, the para-xylene selectivity is 23.9 percent, and the para-xylene product selectivity is 10.5 percent.
[ COMPARATIVE EXAMPLE 3 ]
Mixing a ZSM-5 molecular sieve (provided by Zhongpetrochemical catalyst company and the same below) with a silicon-aluminum molecular ratio of 25 and a binder silicon dioxide (from 40 percent of commercial sodium-free silica sol and the same below), molding, drying, and roasting at 550 ℃ (constant temperature for 3 hours) to obtain a catalyst modified precursor containing 79 weight percent of the ZSM-5 molecular sieve and 21 weight percent of the binder; taking 100.0g of the catalyst precursor, and taking AgNO3Solution (containing AgNO)35.0 percent of weight concentration) 60.0g of the mixture is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃, and continuously taken SnSO4Solution (containing SnSO)410.0% by weight) 60.0g of the mixture was immersed at room temperature for 2 hours in an equal volume, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. The catalyst obtained above was further modified by dipping 40.0g of Dow Corning 550 silicone oil (30 wt% (hereinafter, the same), solvent n-hexane, silicone all commercially available, hereinafter, the same) in an equal volume at 60 ℃ for 5 hours, holding the temperature at 150 ℃ for 10 hours, and calcining at 600 ℃ for 5 hours (calcining in air, hereinafter, the same). And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the hydrogen-hydrocarbon molar ratio is 1.5, the conversion rate of toluene is 38.1 percent, the para-xylene selectivity is 86.1 percent, and the para-xylene product selectivity is 45.0 percent.
[ COMPARATIVE EXAMPLE 4 ]
ZSM-5 molecular sieve (molecular sieve) with silicon-aluminum molecular ratio of 25A catalyst modified precursor containing 79 wt% of a ZSM-5 molecular sieve and 21 wt% of a binder was obtained by mixing, molding, drying, and calcining at 550 ℃ (constant temperature for 3 hours), the following same as that provided by Zhongpetrochemical catalyst company, binder silica (from 40% commercially available sodium-free silica sol, the following same as that) and the mixture; taking 100.0g of the catalyst precursor, and taking Mg (NO)3)2Solution (containing Mg (NO)3)2Weight concentration of 1.5%) 60.0g of the mixture is soaked for 2 hours at normal temperature in equal volume, dried for 6 hours at 120 ℃, and continuously taken SnSO4Solution (containing SnSO)410.0% by weight) 60.0g of the mixture was immersed at room temperature for 2 hours in an equal volume, dried at 120 ℃ for 6 hours, and then calcined at 550 ℃ for 3 hours. The catalyst obtained above was further modified by dipping 40.0g of Dow Corning 550 silicone oil (30 wt% (hereinafter, the same), solvent n-hexane, silicone all commercially available, hereinafter, the same) in an equal volume at 60 ℃ for 5 hours, holding the temperature at 150 ℃ for 10 hours, and calcining at 600 ℃ for 5 hours (calcining in air, hereinafter, the same). And (3) repeating the modification of the silicone oil for 2 times to obtain the catalyst. The catalyst composition is shown in table 1.
The catalyst amount was 15.0 g, and the toluene disproportionation reaction activity and selectivity were examined on a fixed bed reaction evaluation apparatus (all the examples below were evaluated by this method). At a weight space velocity of 4.0h－1Under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 2.8MPa and the hydrogen-hydrocarbon molar ratio is 1.5, the conversion rate of toluene is 33.3 percent, the para-xylene selectivity is 89.1 percent, and the para-xylene product selectivity is 45.1 percent.
TABLE 1 example and comparative catalyst compositions (parts by weight)
Figure BDA0002226501110000191
TABLE 2 comparison of catalyst Performance between examples and comparative examples
Figure BDA0002226501110000201

Claims (11)

1. A selective disproportionation catalyst comprises a molecular sieve, a modifying element, a binder and silicon dioxide, wherein the modifying element comprises a modifying element (1), a modifying element (2) and a modifying element (3), and the components are calculated by weight:
Figure FDA0002226501100000011
wherein the modifying element (1) is Ag and/or Au;
the modifying element (2) is one or more of Ga, Ge, Sn, Bi, Co and Ni;
the modified element (3) is one or more of elements in a second main group;
the aperture of the molecular sieve is 0.50-0.62 nm; the silicon-aluminum molecular ratio of the molecular sieve is 12-100, and preferably 20-70.
2. The selective disproportionation catalyst of claim 1 wherein:
the molecular sieve is at least one of MFI, MEL, MTW and TON structure, preferably at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-22, NU-10 and Theta-1; and/or the presence of a gas in the gas,
the second main group element is one or more of Be, Mg, Ca, Sr and Ba, preferably one or two of Mg and Ca; and/or the presence of a gas in the gas,
the binder is an inert binder, preferably at least one of silicon dioxide, aluminum oxide and clay.
3. A method for preparing the selective disproportionation catalyst according to any of claims 1-2, comprising the steps of:
forming the molecular sieve and a binder, modifying the modified elements and the silicon dioxide, and finally roasting to obtain the selective disproportionation catalyst; wherein the molecular sieve is modified or not by the modifying element.
4. The production method of a selective disproportionation catalyst according to claim 3, characterized in that:
mixing the molecular sieve with a binder, and roasting and forming to obtain a catalyst modified precursor;
wherein the silica modification comprises silica modification of the catalyst modification precursor with a silica modifier;
wherein the modifying element modification comprises at least one of the following steps: 1) modifying the modifying element in the process of preparing the molecular sieve, preferably comprising at least one condition of the modification in the synthesis process of the molecular sieve, the Na exchange process of the molecular sieve or the Na exchange of the molecular sieve; 2) modifying with a modifying element during the shaping of the catalyst modified precursor, and 3) modifying with a modifying element after the shaping of the catalyst modified precursor, including at least one of modifying with a modifying element before the modifying with silica of the catalyst modified precursor, modifying with a modifying element during the modifying with silica of the catalyst modified precursor, and modifying with a modifying element after the modifying with silica of the catalyst modified precursor.
5. The production method of a selective disproportionation catalyst according to claim 3 or 4, characterized in that:
the modification mode of Ag and/or Au elements comprises introducing element sources by one or more modes of impregnation, ion exchange or mixed addition in the process of forming a catalyst modified precursor; and/or the presence of a gas in the gas,
the second main group element modification mode comprises introducing the second main group element by one or more modes of element source impregnation, ion exchange or mixed addition in the catalyst modification precursor forming process; and/or the presence of a gas in the gas,
the Ga, Ge, Sn, Ni, Co and Bi element modification mode comprises one or more modes of introducing Ga, Ge, Sn, Ni, Co and Bi elements through element source impregnation, vapor deposition modification, ion exchange or mixed addition in the catalyst modification precursor forming process.
6. The method for producing a selective disproportionation catalyst according to claim 5, wherein:
the Ag source is at least one of a silver compound solution, a silver salt complex solution and a water-soluble Ag complex solution, preferably at least one of silver nitrate, silver fluoride, silver perchlorate, silver chlorate, an amino complex Ag ion solution, a cyano complex Ag ion solution and a thiosulfate complex Ag ion solution; and/or the presence of a gas in the gas,
the Au source is at least one of gold trichloride and aqua regia diluted solution; and/or the presence of a gas in the gas,
the Ga source is at least one of gallium nitrate, gallium sulfate, gallium halide and gallium ammonium sulfate; and/or the presence of a gas in the gas,
the Ge source is at least one of nitrate, halide and sulfate of germanium; and/or the presence of a gas in the gas,
the Sn source is at least one of nitrate, halide and sulfate of tin; and/or the presence of a gas in the gas,
the Bi source is at least one of nitrate, halide and sulfate of bismuth; and/or the presence of a gas in the gas,
the Ni source is at least one of nitrate, halide and sulfate of nickel; and/or the presence of a gas in the gas,
the Co source is at least one of nitrate, halide and sulfate of cobalt; and/or the presence of a gas in the gas,
the second main group element source is at least one of water-soluble solutions of nitrates, sulfates and halides of the second main group element.
7. The production method of a selective disproportionation catalyst according to claim 3 or 4, characterized in that:
the modification mode of the silicon dioxide comprises introducing the silicon dioxide modifier through one or more modes of impregnation and loading.
8. The method for producing a selective disproportionation catalyst according to claim 7, wherein:
the silicon dioxide modifier is at least one of silicone oil, silane, silicone resin, siloxane and polysiloxane, preferably at least one of silicone oil, methyl silicone oil and phenyl trimethoxy silane.
9. The production method of a selective disproportionation catalyst according to claim 3 or 4, characterized in that:
the roasting is carried out in air or inert gas-containing atmosphere, and the roasting temperature is 300-800 ℃, preferably 450-800 ℃; the roasting time is 0.1-20 hours, preferably 2-20 hours.
10. Use of the selective disproportionation catalyst according to any one of claims 1-2 in selective disproportionation of toluene.
11. Use of a selective disproportionation catalyst in toluene selective disproportionation according to claim 10 wherein:
the reaction is carried out at the reaction temperature of 300-500 ℃, the pressure of 0.1-10 MPa, the hydrogen-hydrocarbon ratio of 0-10 and the weight space velocity of 0.1-10 h-1Under the condition of the reaction.
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