Catalyst for synthesizing durene from unsym-trimethylbenzene
By modifying the catalyst composed of molecular sieve and alumina, the problems of low purity of homotetratoluene and non-renewable catalysts in the prior art are solved, and the efficient and stable conversion of metathylene to homotetratoluene is achieved, which is suitable for large-scale production.
Patent Information
- Application Number
- CN202510412536.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-03
- Publication Date
- 2025-08-15
AI Technical Summary
During the synthesis of homotetratoluene by tri-toluene, existing catalysts have problems such as low purity of homotetratoluene products and the inability to regenerate and use the catalyst, and large-scale production cannot be achieved.
A catalyst composed of modified molecular sieve and alumina is prepared by modifying HZSM-5 or HEU-1 molecular sieve through non-metallic and metallic elements, combining extrusion molding and calcining processes to prepare efficient catalysts.
It improves the conversion rate of tritoluene and homotetratoluene, has good catalyst stability, high product purity, low methanol demand, and can be regenerated and used multiple times.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for synthesizing durene from trimethylbenzene. Background Art
[0002] Durene, an aromatic organic compound, is widely used in the field of organic chemical industry due to its unique molecular structure.
[0003] Traditional durenyl is mainly obtained from the reforming by-product C 10 This method is limited by the low content of tetramethylbenzene in the raw materials and cannot be used for large-scale production.
[0004] In order to solve the above problems, a method for the alkylation of trimethylol to methanol was developed. Since trimethylol and methanol are both relatively large raw materials, they can be produced on a large scale.
[0005] In the process of synthesizing durene by the methanol alkylation of trimethylol, the catalyst plays a decisive role. It can not only significantly improve the yield of durene, but also has a profound impact on the selectivity and efficiency of the reaction.
[0006] The current catalyst for synthesizing durene from trimethylbenzene has many shortcomings, including but not limited to low purity of the obtained durene product and the inability to regenerate the catalyst.
[0007] In view of this, a catalyst for synthesizing durene from trimethylol is designed to solve the above problems. Summary of the Invention
[0008] To solve the problems raised in the above background technology, the present invention provides a catalyst for synthesizing durene from trimethylbenzene, which has high trimethylbenzene conversion rate and durene selectivity, good stability, high purity of the obtained durene product, low methanol demand during the reaction, and the catalyst can be regenerated and used multiple times.
[0009] To achieve the above objectives, the present invention provides the following technical solution: a catalyst for synthesizing durene from trimethylbenzene, comprising the following components by mass fraction: 10-90% of a modified molecular sieve and 10-90% of alumina, wherein the modified molecular sieve is an HZSM-5 molecular sieve or HEU-1 molecular sieve modified with a non-metallic element or a dual-component non-metallic element and a metallic element.
[0010] Furthermore, the specific steps of preparing the catalyst from 10-90% of the modified molecular sieve and 10-90% of alumina include:
[0011] The catalyst is obtained by mixing 10-90% of the modified molecular sieve with 10-90% of alumina or its precursor, extruding the mixture into strips, drying the strips and calcining the strips at 400-580°C.
[0012] Furthermore, the modified molecular sieve is a HZSM-5 molecular sieve or a HEU-1 molecular sieve modified by a non-metallic element, and the specific modification steps include:
[0013] Impregnate HZSM-5 molecular sieve or HEU-1 molecular sieve with ammonium salt or acid solution containing non-metallic elements at 50℃-90℃;
[0014] The impregnated solid is dried and then calcined at 450° C.-550° C. to obtain the modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
[0015] Furthermore, the modified molecular sieve is a HZSM-5 molecular sieve or HEU-1 molecular sieve modified with a dual component of a non-metallic element and a metallic element, and the specific modification steps include:
[0016] The HEU-1 molecular sieve or HZSM-5 molecular sieve is impregnated with an ammonium salt or acid solution containing a non-metallic element at 50°C-90°C, the impregnated solid is dried, and then calcined at 450°C-550°C to obtain a non-metallic element-modified HZSM-5 molecular sieve or HEU-1 molecular sieve;
[0017] The obtained non-metallic element modified HZSM-5 molecular sieve or HEU-1 molecular sieve is subjected to ion exchange with a solution containing a metal element compound at 40°C-90°C, the solid after ion exchange is dried, and then calcined at 450°C-550°C to obtain a non-metallic element and metal element dual-component modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
[0018] Furthermore, the non-metallic element is fluorine, chlorine or phosphorus. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with non-metallic elements, the content of non-metallic elements is 0.5-8%, the fluorine content is 2-3.5%, and the chlorine or phosphorus content is 1-4.5%. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the content of non-metallic elements is 0.5-8%, if it is a modified HZSM-5 molecular sieve, it is 1.5-3%, and if it is a modified HEU-1 molecular sieve, it is 2-6%.
[0019] Furthermore, the ammonium salt solution containing non-metallic elements is NH4F, NH4Cl, (NH4)2HPO4 or (NH4)H2PO4, and the acid solution containing non-metallic elements is HF, HCl or H3PO4, with a concentration of 3-25%.
[0020] Furthermore, the metal element is a rare earth metal, Ag or an alkaline earth metal, wherein the rare earth metal is Ce and / or La, and the alkaline earth metal is Mg. In the process of modifying the HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the metal element content is 0.5-6%, if it is a modified HZSM-5 molecular sieve, it is 0.5-3%, and if it is a modified HEU-1 molecular sieve, it is 0.7-3%.
[0021] Furthermore, the metal element-containing compound is a nitrate or chloride of a rare earth metal, Ag or an alkaline earth metal, with a concentration of 2-10%.
[0022] Furthermore, the silicon oxide / aluminum oxide molar ratio of the HZSM-5 molecular sieve is 20-48, and the silicon oxide / aluminum oxide molar ratio of the HEU-1 molecular sieve is 25-70.
[0023] Furthermore, the precursor of the aluminum oxide is one or more of aluminum sol, aluminum gel and pseudo-boehmite.
[0024] Compared with the prior art, the present invention has the following beneficial effects:
[0025] The method has high conversion rate of trimethylol and selectivity of durenes and good stability; the obtained durenes product has high purity; the methanol demand during the reaction is low; and the catalyst can be regenerated and used multiple times. DETAILED DESCRIPTION
[0026] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.
[0027] The present invention provides the following technical solution: a catalyst for synthesizing durene from trimethylbenzene, comprising the following components by mass fraction: 10-90% of a modified molecular sieve and 10-90% of aluminum oxide, wherein the modified molecular sieve is an HZSM-5 molecular sieve or HEU-1 molecular sieve modified with a non-metallic element or a non-metallic element and a metallic element.
[0028] Specifically, the specific steps of preparing the catalyst with 10-90% of modified molecular sieve and 10-90% of alumina include:
[0029] The catalyst is obtained by mixing 10-90% of the modified molecular sieve with 10-90% of alumina or its precursor, extruding the mixture into strips, drying the strips and calcining the strips at 400-580°C.
[0030] Specifically, the modified molecular sieve is a HZSM-5 molecular sieve or a HEU-1 molecular sieve modified with a non-metallic element, and the specific modification steps include:
[0031] Impregnate HZSM-5 molecular sieve or HEU-1 molecular sieve with ammonium salt or acid solution containing non-metallic elements at 50℃-90℃;
[0032] The impregnated solid is dried and then calcined at 450° C.-550° C. to obtain the modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
[0033] Specifically, the modified molecular sieve is a HZSM-5 molecular sieve or a HEU-1 molecular sieve modified with a non-metallic element and a metallic element. The specific modification steps include:
[0034] The HEU-1 molecular sieve or HZSM-5 molecular sieve is impregnated with an ammonium salt or acid solution containing a non-metallic element at 50°C-90°C, the impregnated solid is dried, and then calcined at 450°C-550°C to obtain a non-metallic element-modified HZSM-5 molecular sieve or HEU-1 molecular sieve;
[0035] The obtained non-metallic element modified HZSM-5 molecular sieve or HEU-1 molecular sieve is subjected to ion exchange with a solution containing a metal element compound at 40°C-90°C, the solid after ion exchange is dried, and then calcined at 450°C-550°C to obtain a non-metallic element and metal element dual-component modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
[0036] Specifically, the non-metallic element is fluorine, chlorine or phosphorus. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with non-metallic elements, the content of non-metallic elements is 0.5-8%, the fluorine content is 2-3.5%, and the chlorine or phosphorus content is 1-4.5%. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the content of non-metallic elements is 0.5-8%, if it is a modified HZSM-5 molecular sieve, it is 1.5-3%, and if it is a modified HEU-1 molecular sieve, it is 2-6%.
[0037] Specifically, the ammonium salt solution containing non-metallic elements is NH4F, NH4Cl, (NH4)2HPO4 or (NH4)H2PO4, and the acid solution containing non-metallic elements is HF, HCl or H3PO4, with a concentration of 3-25%.
[0038] Specifically, the metal element is a rare earth metal, Ag or an alkaline earth metal, wherein the rare earth metal is Ce and / or La, and the alkaline earth metal is Mg. In the process of modifying the HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the metal element content is 0.5-6%, if it is a modified HZSM-5 molecular sieve, it is 0.5-3%, and if it is a modified HEU-1 molecular sieve, it is 0.7-3%.
[0039] Specifically, the metal element-containing compound is a nitrate or chloride of a rare earth metal, Ag or an alkaline earth metal, with a concentration of 2-10%.
[0040] Specifically, the silica / alumina molar ratio of the HZSM-5 molecular sieve is 20-48, and the silica / alumina molar ratio of the HEU-1 molecular sieve is 25-70.
[0041] Specifically, the precursor of alumina is one or more of alumina sol, alumina gel and pseudo-boehmite.
[0042] The following is described with specific embodiments:
[0043] Example 1
[0044] Preparation of modified HZSM-5 molecular sieve:
[0045] A HZSM-5 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 42 was taken and impregnated with a 15% NH4F solution at 80°C for 2 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HZSM-5 molecular sieve a.
[0046] The X-ray fluorescence spectrum (XRF) of fluorine-modified HZSM-5 molecular sieve a showed that the F content was 5.71%.
[0047] Preparation of catalyst:
[0048] The fluorine-modified HZSM-5 molecular sieve a was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry weight ratio of 65:35, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-1.
[0049] X-ray fluorescence spectrum (XRF) analysis of catalyst C-1 showed that it contained 65% of fluorine-modified HZSM-5 molecular sieve a and 35% of aluminum oxide.
[0050] Example 2
[0051] Preparation of modified HZSM-5 molecular sieve:
[0052] HZSM-5 molecular sieve with a molar ratio of silica to alumina of 38 was taken and impregnated with a 5% (NH4)2HPO4 solution at 90°C for 1 hour with stirring. The liquid / solid mass ratio of the impregnation was 7:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain phosphorus-modified HZSM-5 molecular sieve b.
[0053] The X-ray fluorescence spectrum (XRF) of phosphorus-modified HZSM-5 molecular sieve b was analyzed, and the results showed that the P content was 1.33%;
[0054] Preparation of catalyst:
[0055] The prepared phosphorus-modified HZSM-5 molecular sieve b was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry basis weight ratio of 65:35, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-2.
[0056] X-ray fluorescence spectrum (XRF) analysis of catalyst C-2 showed that it contained 65% of phosphorus-modified HZSM-5 molecular sieve b and 35% of alumina.
[0057] Example 3
[0058] Preparation of modified HZSM-5 molecular sieve:
[0059] Chlorine-modified HZSM-5 molecular sieve c was obtained by stirring an HZSM-5 molecular sieve with a silica / alumina molar ratio of 42 and impregnating it with a 4% NH4Cl solution at 85°C for 0.5 h at a liquid / solid ratio of 6:1. The impregnated solid was dried at 110°C for 4 h and calcined at 500°C for 6 h.
[0060] The X-ray fluorescence spectrum (XRF) of the chlorine-modified HZSM-5 molecular sieve c showed that the Cl content was 4.35%.
[0061] Preparation of catalyst:
[0062] The chlorine-modified HZSM-5 molecular sieve c was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry weight ratio of 65:35, and then 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-3.
[0063] X-ray fluorescence spectrum (XRF) analysis of catalyst C-3 showed that it contained 65% of chlorine-modified HZSM-5 molecular sieve c and 35% of alumina.
[0064] Example 4
[0065] Preparation of modified HZSM-5 molecular sieve:
[0066] HZSM-5 molecular sieve with a molar ratio of silica to alumina of 42 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HZSM-5 molecular sieve d;
[0067] The X-ray fluorescence spectrum (XRF) of fluorine-modified HZSM-5 molecular sieve d showed that the F content was 2.63%.
[0068] Preparation of catalyst:
[0069] The fluorine-modified HZSM-5 molecular sieve d was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry weight ratio of 65:35, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-4.
[0070] X-ray fluorescence spectrum (XRF) analysis of catalyst C-4 showed that it contained 65% of fluorine-modified HZSM-5 molecular sieve d and 35% of alumina.
[0071] Example 5
[0072] Preparation of modified HZSM-5 molecular sieve:
[0073] A HZSM-5 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 25 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HZSM-5 molecular sieve e.
[0074] The X-ray fluorescence spectrum (XRF) of fluorine-modified HZSM-5 molecular sieve e was analyzed, and the results showed that the F element content was 2.78%;
[0075] Preparation of catalyst:
[0076] The fluorine-modified HZSM-5 molecular sieve e was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry basis weight ratio of 60:40, and diluted nitric acid with a concentration of 1% was added and kneaded, with the diluted nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-5.
[0077] X-ray fluorescence spectrum (XRF) analysis of catalyst C-5 showed that it contained 60% fluorine-modified HZSM-5 molecular sieve e and 40% alumina.
[0078] Example 6
[0079] Preparation of modified HZSM-5 molecular sieve:
[0080] A HZSM-5 molecular sieve with a molar ratio of silica to alumina of 38 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HZSM-5 molecular sieve f.
[0081] The X-ray fluorescence spectrum (XRF) of fluorine-modified HZSM-5 molecular sieve f was analyzed, and the results showed that the F element content was 3.08%;
[0082] Preparation of catalyst:
[0083] The fluorine-modified HZSM-5 molecular sieve f was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry weight ratio of 60:40, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-6.
[0084] X-ray fluorescence spectrum (XRF) analysis of catalyst C-6 showed that it contained 60% fluorine-modified HZSM-5 molecular sieve f and 40% alumina.
[0085] Example 7
[0086] Preparation of modified HZSM-5 molecular sieve:
[0087] HZSM-5 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 46 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HZSM-5 molecular sieve g;
[0088] The X-ray fluorescence spectrum (XRF) of fluorine-modified HZSM-5 molecular sieve g was analyzed, and the results showed that the F content was 3.21%;
[0089] Preparation of catalyst:
[0090] The fluorine-modified HZSM-5 molecular sieve g was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand PuralSB) at a dry basis weight ratio of 60:40, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-7.
[0091] X-ray fluorescence spectrum (XRF) analysis of catalyst C-7 showed that it contained 60% fluorine-modified HZSM-5 molecular sieve g and 40% alumina.
[0092] Example 8
[0093] Preparation of two-component modified HZSM-5 molecular sieve:
[0094] HZSM-5 molecular sieve with a molar ratio of silica to alumina of 42 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HZSM-5 molecular sieve d;
[0095] The prepared fluorine-modified HZSM-5 molecular sieve d was ion-exchanged with a 4% La(NO3)3 solution at 80°C for 1.5 h. The liquid / solid mass ratio of the ion exchange was 10:1. The solid after ion exchange was dried at 110°C for 4 h and calcined at 520°C for 5 h to obtain fluorine- and La-modified HZSM-5 molecular sieve h.
[0096] The X-ray fluorescence spectrum (XRF) of the fluorine and La-modified HZSM-5 molecular sieve h showed that the F content was 2.63% and the La content was 1.83%.
[0097] Preparation of catalyst:
[0098] The prepared fluorine- and La-modified HZSM-5 molecular sieve h was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounts for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-8.
[0099] X-ray fluorescence spectrum (XRF) analysis of catalyst C-8 showed that it contained 65% of modified HZSM-5 molecular sieve h and 35% of alumina.
[0100] Example 9
[0101] Preparation of two-component modified HZSM-5 molecular sieve:
[0102] HZSM-5 molecular sieve with a molar ratio of silica to alumina of 42 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HZSM-5 molecular sieve d;
[0103] The prepared fluorine-modified HZSM-5 molecular sieve d was ion-exchanged with a 5% AgNO3 solution at 80°C for 2 h, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4 h and calcined at 520°C for 5 h to obtain fluorine- and Ag-modified HZSM-5 molecular sieve j.
[0104] The X-ray fluorescence spectrum (XRF) of the fluorine and Ag modified HZSM-5 molecular sieve j showed that the F content was 2.63% and the Ag content was 2.82%.
[0105] Preparation of catalyst:
[0106] The prepared fluorine- and Ag-modified HZSM-5 molecular sieve j was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-9.
[0107] X-ray fluorescence (XRF) analysis of catalyst C-9 showed that it contained 65% fluorine and Ag-modified HZSM-5 molecular sieve j and 35% alumina.
[0108] Example 10
[0109] Preparation of two-component modified HZSM-5 molecular sieve:
[0110] HZSM-5 molecular sieve with a molar ratio of silica to alumina of 42 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring, and the liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HZSM-5 molecular sieve d;
[0111] The prepared fluorine-modified HZSM-5 molecular sieve d was ion-exchanged with a 4% Ce(NO3)3 solution at 80°C for 1 h, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4 h and calcined at 520°C for 5 h to obtain fluorine- and Ce-modified HZSM-5 molecular sieve k.
[0112] The X-ray fluorescence spectrum (XRF) of the fluorine and Ce modified HZSM-5 molecular sieve k showed that the F content was 2.63% and the Ce content was 1.35%.
[0113] Preparation of catalyst:
[0114] The prepared fluorine- and Ce-modified HZSM-5 molecular sieve k was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35. The mixture was then added with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder, and kneaded. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-10.
[0115] X-ray fluorescence (XRF) analysis of catalyst C-10 showed that it contained 65% of fluorine and Ce-modified HZSM-5 molecular sieve k and 35% of alumina.
[0116] Example 11
[0117] Preparation of modified HEU-1 molecular sieve:
[0118] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 15% NH4F solution at 80°C for 2 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HEU-1 molecular sieve l.
[0119] The X-ray fluorescence spectrum (XRF) of fluorine-modified HEU-1 molecular sieve l showed that the F content was 5.32%;
[0120] Preparation of catalyst:
[0121] The prepared fluorine-modified HEU-1 molecular sieve 1 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-11.
[0122] X-ray fluorescence (XRF) analysis of catalyst C-11 showed that it contained 65% of fluorine-modified HEU-1 molecular sieve 1 and 35% of alumina.
[0123] Example 12
[0124] Preparation of modified HEU-1 molecular sieve:
[0125] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 35 was taken and impregnated with a 5% (NH4)2HPO4 solution at 90°C for 1 hour with stirring. The liquid / solid mass ratio of the impregnation was 7:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain phosphorus-modified HEU-1 molecular sieve m;
[0126] The X-ray fluorescence spectrum (XRF) of phosphorus-modified HEU-1 molecular sieve m was analyzed, and the results showed that the P element content was 1.26%;
[0127] Preparation of catalyst:
[0128] The prepared phosphorus-modified HEU-1 molecular sieve m was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounts for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-12.
[0129] X-ray fluorescence spectrum (XRF) analysis of catalyst C-12 showed that it contained 65% of phosphorus-modified HEU-1 molecular sieve m and 35% of alumina.
[0130] Example 13
[0131] Preparation of modified HEU-1 molecular sieve:
[0132] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 4% NH4Cl solution at 85°C for 0.5h with stirring. The liquid / solid mass ratio of the impregnation was 6:1. The impregnated solid was dried at 110°C for 4h and calcined at 500°C for 6h to obtain chlorine-modified HEU-1 molecular sieve n.
[0133] The X-ray fluorescence spectrum (XRF) of chlorine-modified HEU-1 molecular sieve n was analyzed, and the results showed that the Cl element content was 4.43%;
[0134] Preparation of catalyst:
[0135] The prepared chlorine-modified HEU-1 molecular sieve n was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-13.
[0136] X-ray fluorescence spectrum (XRF) analysis of catalyst C-13 showed that it contained 65% of chlorine-modified HEU-1 molecular sieve n and 35% of alumina.
[0137] Example 14
[0138] Preparation of modified HEU-1 molecular sieve:
[0139] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HEU-1 molecular sieve o;
[0140] The X-ray fluorescence spectrum (XRF) of fluorine-modified HEU-1 molecular sieve o was analyzed, and the results showed that the F element content was 2.75%;
[0141] Preparation of catalyst:
[0142] The prepared fluorine-modified HEU-1 molecular sieve o was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis mass ratio of 65:35, and diluted nitric acid with a concentration of 1% was added and kneaded, with the added diluted nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-14.
[0143] X-ray fluorescence spectrum (XRF) analysis of catalyst C-14 showed that it contained 65% of fluorine-modified HEU-1 molecular sieve and 35% of aluminum oxide.
[0144] Example 15
[0145] Preparation of modified HEU-1 molecular sieve:
[0146] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 25 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HEU-1 molecular sieve p.
[0147] The X-ray fluorescence spectrum (XRF) of fluorine-modified HEU-1 molecular sieve p showed that the F content was 2.72%;
[0148] Preparation of catalyst:
[0149] The prepared fluorine-modified HEU-1 molecular sieve p was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 60:40, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-15.
[0150] X-ray fluorescence spectrum (XRF) analysis of catalyst C-15 showed that it contained 60% of fluorine-modified HEU-1 molecular sieve p and 40% of alumina.
[0151] Example 16
[0152] Preparation of modified HEU-1 molecular sieve:
[0153] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 35 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HEU-1 molecular sieve q.
[0154] The X-ray fluorescence spectrum (XRF) of fluorine-modified HEU-1 molecular sieve q was analyzed, and the results showed that the F element content was 3.17%;
[0155] Preparation of catalyst:
[0156] The prepared fluorine-modified HEU-1 molecular sieve q was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 60:40, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-16.
[0157] X-ray fluorescence spectrum (XRF) analysis of catalyst C-16 showed that it contained 60% of fluorine-modified HEU-1 molecular sieve q and 40% of alumina.
[0158] Embodiment 17
[0159] Preparation of modified HEU-1 molecular sieve:
[0160] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 50 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain fluorine-modified HEU-1 molecular sieve r.
[0161] The X-ray fluorescence spectrum (XRF) of fluorine-modified HEU-1 molecular sieve r was analyzed, and the results showed that the F element content was 3.11%;
[0162] Preparation of catalyst:
[0163] The prepared fluorine-modified HEU-1 molecular sieve r was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 60:40, and 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-17.
[0164] X-ray fluorescence spectrum (XRF) analysis of catalyst C-17 showed that it contained 60% fluorine-modified HEU-1 molecular sieve r and 40% alumina.
[0165] Embodiment 18
[0166] Preparation of two-component modified HEU-1 molecular sieve:
[0167] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HEU-1 molecular sieve.
[0168] The prepared fluorine-modified HEU-1 molecular sieve was ion-exchanged with a 4% La(NO3)3 solution at 80°C for 1.5h, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4h and calcined at 520°C for 5h to obtain fluorine- and La-modified HEU-1 molecular sieves.
[0169] The X-ray fluorescence spectrum (XRF) of the fluorine and La modified HEU-1 molecular sieves showed that the F content was 2.75% and the La content was 1.88%.
[0170] Preparation of catalyst:
[0171] The prepared fluorine- and La-modified HEU-1 molecular sieve s was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-18.
[0172] X-ray fluorescence (XRF) analysis of the catalyst C-18 showed that it contained 65% of fluorine- and La-modified HEU-1 molecular sieves and 35% of alumina.
[0173] Example 19
[0174] Preparation of two-component modified HEU-1 molecular sieve:
[0175] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HEU-1 molecular sieve.
[0176] The prepared fluorine-modified HEU-1 molecular sieve was ion-exchanged with a 5% Mg(NO3)2 solution at 80°C for 2 hours, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4 hours and calcined at 520°C for 5 hours to obtain fluorine- and Mg-modified HEU-1 molecular sieve t;
[0177] The X-ray fluorescence spectrum (XRF) of the fluorine and Mg modified HEU-1 molecular sieve t showed that the F content was 2.75% and the Mg content was 1.03%.
[0178] Preparation of catalyst:
[0179] The prepared fluorine- and Mg-modified HEU-1 molecular sieve t was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounts for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-19.
[0180] X-ray fluorescence (XRF) analysis of catalyst C-19 showed that it contained 65% of fluorine- and Mg-modified HEU-1 molecular sieve t and 35% of alumina.
[0181] Example 20
[0182] Preparation of two-component modified HEU-1 molecular sieve:
[0183] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 40 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HEU-1 molecular sieve.
[0184] The prepared fluorine-modified HEU-1 molecular sieve was ion-exchanged with a 4% Ce(NO3)3 solution at 80°C for 1 hour. The liquid / solid mass ratio of the ion exchange was 10:1. The solid after ion exchange was dried at 110°C for 4 hours and calcined at 520°C for 5 hours to obtain fluorine- and Ce-modified HEU-1 molecular sieve u.
[0185] The X-ray fluorescence spectrum (XRF) of the fluorine and Ce modified HEU-1 molecular sieve u showed that the F content was 2.75% and the Ce content was 1.28%.
[0186] Preparation of catalyst:
[0187] The prepared fluorine and Ce modified HEU-1 molecular sieve u was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 65:35, and then 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-20.
[0188] X-ray fluorescence (XRF) analysis of catalyst C-20 showed that it contained 65% of fluorine and Ce-modified HEU-1 molecular sieve u and 35% of alumina.
[0189] Example 21
[0190] Preparation of two-component modified HEU-1 molecular sieve:
[0191] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 50 was taken and impregnated with a 10% NH4F solution at 70°C for 1.5 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HEU-1 molecular sieve.
[0192] The X-ray fluorescence spectrum (XRF) of the fluorine-modified HEU-1 molecular sieve showed that the F content was 3.11%.
[0193] The prepared fluorine-modified HEU-1 molecular sieve o was ion-exchanged with a 4% Ce(NO3)3 solution at 80°C for 1 hour, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4 hours and calcined at 520°C for 5 hours to obtain fluorine- and Ce-modified HEU-1 molecular sieve v.
[0194] The X-ray fluorescence spectrum (XRF) of the fluorine and Ce modified HEU-1 molecular sieve v showed that the F content was 3.21% and the Ce content was 1.79%.
[0195] Preparation of catalyst:
[0196] The prepared fluorine- and Ce-modified HEU-1 molecular sieve v was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 60:40, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounts for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-21.
[0197] X-ray fluorescence (XRF) analysis of catalyst C-21 showed that it contained 60% of fluorine and Ce-modified HEU-1 molecular sieve v and 40% of alumina.
[0198] Example 22
[0199] Preparation of two-component modified HEU-1 molecular sieve:
[0200] HEU-1 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 35 was taken and impregnated with a 15% NH4F solution at 80°C for 2 hours with stirring. The liquid / solid mass ratio of the impregnation was 5:1. The impregnated solid was dried at 110°C for 4 hours and calcined at 500°C for 6 hours to obtain a fluorine-modified HEU-1 molecular sieve.
[0201] The X-ray fluorescence spectrum (XRF) analysis of the fluorine-modified HEU-1 molecular sieve showed that the F content was 5.15%.
[0202] The prepared fluorine-modified HEU-1 molecular sieve was ion-exchanged with a 2% Ce(NO3)3 solution at 80°C for 2h, with a liquid / solid mass ratio of 10:1. The solid after ion exchange was dried at 110°C for 4h and calcined at 520°C for 5h to obtain fluorine- and Ce-modified HEU-1 molecular sieve w.
[0203] The X-ray fluorescence spectrum (XRF) of the fluorine and Ce modified HEU-1 molecular sieve w showed that the F content was 5.32% and the Ce content was 1.08%.
[0204] Preparation of catalyst:
[0205] The prepared fluorine- and Ce-modified HEU-1 molecular sieve w was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry basis weight ratio of 60:40, and then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounts for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst C-22.
[0206] X-ray fluorescence (XRF) analysis of catalyst C-22 showed that it contained 60% of fluorine and Ce-modified HEU-1 molecular sieve w and 40% of alumina.
[0207] Comparative Example 1
[0208] HZSM-5 molecular sieve with a silica / alumina molar ratio of 42 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-1.
[0209] X-ray fluorescence spectrum (XRF) analysis of catalyst D-1 showed that it contained 65% of HZSM-5 molecular sieve and 35% of alumina.
[0210] Comparative Example 2
[0211] HZSM-5 molecular sieve with a silica / alumina molar ratio of 38 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-2.
[0212] X-ray fluorescence spectrum (XRF) analysis of catalyst D-2 showed that it contained 65% of HZSM-5 molecular sieve and 35% of alumina.
[0213] Comparative Example 3
[0214] HZSM-5 molecular sieve with a silica / alumina molar ratio of 46 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 60:40. 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-3.
[0215] X-ray fluorescence spectrum (XRF) analysis of catalyst D-3 showed that it contained 60% HZSM-5 molecular sieve and 40% alumina.
[0216] Comparative Example 4
[0217] HZSM-5 molecular sieve with a silica / alumina molar ratio of 42 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. 1% dilute nitric acid was added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours.
[0218] At 450℃ and a water vapor space velocity of 1h -1 The mixture was treated under the conditions of 400 nm and 100 nm for 3 h. After stopping the water flow, the temperature was kept constant and purged with air for 5 h to cool to room temperature to obtain catalyst D-4.
[0219] X-ray fluorescence spectrum (XRF) analysis of catalyst D-4 showed that it contained 65% of HZSM-5 molecular sieve and 35% of alumina.
[0220] Comparative Example 5
[0221] HZSM-5 molecular sieve with a silica / alumina molar ratio of 60 and beta molecular sieve with a silica / alumina molar ratio of 20 are mixed in a mass ratio of 2:1, and then mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) in a dry basis mass ratio of 70:30. Dilute nitric acid with a concentration of 1% is added and kneaded, with the added dilute nitric acid accounting for 50% of the solid powder. The mixture is extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain a mixed molecular sieve containing 70% and 30% alumina solid.
[0222] At 600℃ and a water vapor space velocity of 1h -1 Treat for 3 hours under the conditions of , stop the water flow, keep the temperature unchanged, and blow with air for 5 hours to cool down to room temperature;
[0223] The catalyst was modified by impregnation with a 10% NH4F and 4% Ce(NO3)3 solution at 70°C for 1.5 h. The impregnated solid was dried at 110°C for 4 h and calcined at 550°C for 2 h to obtain catalyst D-5.
[0224] X-ray fluorescence spectrum (XRF) analysis of catalyst D-5 showed that the F content was 2.55% and the Ce content was 0.95%.
[0225] Comparative Example 6
[0226] Take HZSM-5 molecular sieve with a molar ratio of silicon oxide to aluminum oxide of 42, and use 0.5 mol / L HCl solution for pickling. Heat the solution to 100 ° C and slowly cool it to room temperature after 3 hours. The liquid / solid mass ratio of pickling is 1.2:1. Wash the solid after pickling with deionized water until no Cl is detected in the washing liquid. -1 , obtaining the acid-washed molecular sieve;
[0227] The acid-washed molecular sieve was calcined at 540°C for 3 h, and steam was introduced during the calcination at a space velocity of 1 h. -1 , stop heating and stop introducing water vapor at the same time, purge with air to cool down to room temperature;
[0228] The calcined molecular sieve was impregnated with 8% Ce(NO3)3 solution at 100℃ for 3h to carry out rare earth modification. The liquid / solid mass ratio of the impregnation was 1.3:1. After impregnation, it was slowly cooled to room temperature, dried, and calcined.
[0229] The calcination conditions are as follows: first, the temperature is raised from room temperature to 100°C for 10 minutes, then from 100°C to 350°C for 100 minutes, then from 350°C to 540°C for 50 minutes, and then calcined at 540°C for 3 hours to obtain catalyst D-6.
[0230] X-ray fluorescence spectrum (XRF) analysis of catalyst D-6 showed that the Ce element content was 1.83%.
[0231] Comparative Example 7
[0232] HEU-1 molecular sieve with a silica / alumina molar ratio of 40 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. The mixture was then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-7.
[0233] X-ray fluorescence spectrum (XRF) analysis of catalyst D-7 showed that it contained 65% of HEU-1 molecular sieve and 35% of alumina.
[0234] Comparative Example 8
[0235] HEU-1 molecular sieve with a silica / alumina molar ratio of 35 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 60:40. The mixture was then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-8.
[0236] X-ray fluorescence spectrum (XRF) analysis of catalyst D-8 showed that it contained 60% of HEU-1 molecular sieve and 40% of alumina.
[0237] Comparative Example 9
[0238] HEU-1 molecular sieve with a silica / alumina molar ratio of 50 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. The mixture was then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain catalyst D-9.
[0239] X-ray fluorescence spectrum (XRF) analysis of catalyst D-9 showed that it contained 65% of HEU-1 molecular sieve and 35% of alumina.
[0240] Comparative Example 10
[0241] HEU-1 molecular sieve with a silica / alumina molar ratio of 40 was mixed with pseudo-boehmite powder (produced by Condea, Germany, brand Pural SB) at a dry weight ratio of 65:35. The mixture was then kneaded with 1% dilute nitric acid, where the added dilute nitric acid accounted for 50% of the solid powder. The mixture was extruded into strips, dried at 110°C for 4 hours, and calcined at 540°C for 5 hours to obtain the catalyst.
[0242] At 450℃ and a water vapor space velocity of 1h -1 After the water supply was stopped, the temperature was kept constant and purged with air for 5 hours to cool to room temperature to obtain catalyst D-10;
[0243] X-ray fluorescence spectrum (XRF) analysis of catalyst D-10 showed that it contained 65% of HEU-1 molecular sieve and 35% of alumina.
[0244] 5 g of the catalysts of the above examples and comparative examples were sequentially loaded into the reaction tube of a microreactor, and trimethylol and methanol were added to the reaction tube using N2 as a carrier gas to carry out an alkylation reaction to produce durene;
[0245] The reaction conditions are as follows: carrier gas flow rate of 60 mL / min, temperature of 330°C, pressure of 0.5 MPa, mass space velocity of the reaction raw material feed of 1.2 h-1, and molar ratio of trimethylol to methanol feed of 2:1;
[0246] The catalysts used in the examples and comparative examples and the results of the single-pass reactions are shown in the following tables:
[0247]
[0248]
[0249]
[0250]
[0251]
[0252] In the above table, the reaction evaluation results are calculated as follows:
[0253] Durene yield = trimethylol conversion × durene selectivity × 100%
[0254] As can be seen from the above table, the conversion rate of trimethylolbenzene and the selectivity of durene in the present application are high and the stability is good. The obtained durene product has high purity, the methanol demand during the reaction is low, and the catalyst can be regenerated and used multiple times.
[0255] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.
Claims
1. A catalyst for synthesizing durene from trimethylol, characterized in that: The invention is composed of the following components in mass fraction: 10-90% of modified molecular sieve and 10-90% of aluminum oxide, wherein the modified molecular sieve is HZSM-5 molecular sieve or HEU-1 molecular sieve modified by non-metallic elements or non-metallic elements and metal elements.
2. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 1, wherein: The specific steps of preparing the catalyst from 10-90% of the modified molecular sieve and 10-90% of the aluminum oxide include: The catalyst is obtained by mixing 10-90% of the modified molecular sieve with 10-90% of alumina or its precursor, extruding the mixture into strips, drying the strips and calcining the strips at 400-580°C.
3. A catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 2, characterized in that: The modified molecular sieve is a HZSM-5 molecular sieve or a HEU-1 molecular sieve modified with a non-metallic element, and the specific modification steps include: Impregnate HZSM-5 molecular sieve or HEU-1 molecular sieve with ammonium salt or acid solution containing non-metallic elements at 50℃-90℃; The impregnated solid is dried and then calcined at 450° C. to 550° C. to obtain the modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
4. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 3, wherein: The modified molecular sieve is a HZSM-5 molecular sieve or HEU-1 molecular sieve modified with a double component of a non-metallic element and a metallic element. The specific modification steps include: The HEU-1 molecular sieve or HZSM-5 molecular sieve is impregnated with an ammonium salt or acid solution containing a non-metallic element at 50°C-90°C, the impregnated solid is dried, and then calcined at 450°C-550°C to obtain a non-metallic element-modified HZSM-5 molecular sieve or HEU-1 molecular sieve; The obtained non-metallic element modified HZSM-5 molecular sieve or HEU-1 molecular sieve is subjected to ion exchange with a solution containing a metal element compound at 40°C-90°C, the solid after ion exchange is dried, and then calcined at 450°C-550°C to obtain a non-metallic element and metal element dual-component modified HZSM-5 molecular sieve or HEU-1 molecular sieve.
5. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 4, characterized in that: The non-metallic element is fluorine, chlorine or phosphorus. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with non-metallic elements, the content of non-metallic elements is 0.5-8%, the content of fluorine is 2-3.5%, and the content of chlorine or phosphorus is 1-4.5%. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the content of non-metallic elements is 0.5-8%, if it is a modified HZSM-5 molecular sieve, it is 1.5-3%, and if it is a modified HEU-1 molecular sieve, it is 2-6%.
6. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 5, characterized in that: The ammonium salt solution containing non-metallic elements is NH4F, NH4Cl, (NH4)2HPO4 or (NH4) H2PO4, the acid solution containing non-metallic elements is HF, HCl or H3PO4, with a concentration of 3-25%.
7. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 6, characterized in that: The metal element is a rare earth metal, Ag or an alkaline earth metal, wherein the rare earth metal is Ce and / or La, and the alkaline earth metal is Mg. In the process of modifying HZSM-5 molecular sieve or HEU-1 molecular sieve with two components of non-metallic elements and metal elements, the metal element content is 0.5-6%, if it is a modified HZSM-5 molecular sieve, it is 0.5-3%, and if it is a modified HEU-1 molecular sieve, it is 0.7-3%.
8. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 7, characterized in that: The metal element-containing compound is a nitrate or chloride of a rare earth metal, Ag or an alkaline earth metal, with a concentration of 2-10%.
9. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 8, characterized in that: The silicon oxide / aluminum oxide molar ratio of the HZSM-5 molecular sieve is 20-48, and the silicon oxide / aluminum oxide molar ratio of the HEU-1 molecular sieve is 25-70.
10. The catalyst for synthesizing durene from unsymmetrical trimethylbenzene according to claim 9, characterized in that: The precursor of the aluminum oxide is one or more of aluminum sol, aluminum gel and pseudo-boehmite.