Silicon modified octane number additive based on ZMQ-1 molecular sieve and preparation method of silicon modified octane number additive
By infrared steam baking and silane coupling agent modification on the ZMQ-1 molecular sieve, silicon modified ZMQ-1 molecular sieve was prepared, and combined with modified clay and binder, silicon modified octane additives were prepared based on ZMQ-1 molecular sieve, which solved the problem of difficult to increase the gasoline octane number and olefin content in the prior art, and achieved the effect of increasing the gasoline octane number and reducing coke formation.
Patent Information
- Application Number
- CN202510122610.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-24
- Publication Date
- 2025-05-30
AI Technical Summary
When existing catalysts produce gasoline in catalytic cracking, gasoline yield and octane number are usually not high, and it is difficult to increase gasoline octane number and reduce olefin content and coke formation without reducing gasoline yield.
Silicon-modified ZMQ-1 molecular sieve was prepared by infrared steam baking and silane coupling agent modification, and silicon modified octane additives were prepared by metal oxide and cetyl trimethylammonium chloride modified clay, combined with binder and pseudo-thin aluminite, silicon-modified octane additives based on ZMQ-1 molecular sieve were prepared.
It is achieved to increase the gasoline octane number, reduce the gasoline olefin content and reduce coke generation without reducing the gasoline yield, and improve the overall efficiency of the catalytic cracking process.
Smart Images
Figure BDA0005259352210000061
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of molecular sieves, and particularly relates to a silicon-modified octane enhancer based on ZMQ-1 molecular sieve and a preparation method thereof. Background Art
[0002] When ordinary catalysts are used for catalytic cracking to produce gasoline, the gasoline yield and its octane number are usually not high, and an octane enhancer needs to be added. An octane enhancer is an additive used to increase the octane number of catalytic cracking gasoline. It is used in combination with the main catalyst and generally can increase the octane number (RON) by 2 - 4 units.
[0003] Currently, most octane enhancers use silicon-modified ZSM-5 molecular sieves as the main active component to increase the octane number of gasoline without reducing the gasoline yield.
[0004] CN 118515294 A discloses a ZMQ-1 molecular sieve. It contains a three-dimensional pore system composed of 28×10×10 yuan rings, and the size of the 28MR has reached the mesoporous size range. This is the first structurally stable aluminosilicate molecular sieve with intrinsic mesopores. This molecular sieve has high thermal and hydrothermal stability, abundant B acid sites and medium to high B acid strength.
[0005] Currently, there is little research on the above ZMQ-1 molecular sieve. Through modification of it, the present invention realizes increasing the gasoline yield while increasing the octane number of gasoline, reducing the olefin content of gasoline and reducing coke formation.
[0006] Based on this, the present invention designs a silicon-modified octane enhancer based on ZMQ-1 molecular sieve and a preparation method thereof to solve the above problems. Summary of the Invention
[0007] In view of the above-mentioned drawbacks of the prior art, the present invention provides a silicon-modified octane enhancer based on ZMQ-1 molecular sieve and a preparation method thereof.
[0008] To achieve the above objectives, the present invention is realized through the following technical solutions:
[0009] The silicon-modified octane enhancer based on ZMQ-1 molecular sieve, in parts by weight, contains 15 - 50 parts of modified ZMQ-1 molecular sieve, 5 - 30 parts of clay, 5 - 25 parts of pseudoboehmite, and 6 - 12 parts of binder; wherein, the modified ZMQ-1 molecular sieve is obtained by modification with sodium silicate and silane coupling agent; the clay is obtained by modification with cetyltrimethylammonium chloride and metal oxide, and the metal oxide content in the clay is 1 - 5%; the cetyltrimethylammonium chloride content is 0.3 - 1%.
[0010] Furthermore, the metal oxide contains at least one metal element among V, Ti, and Mo, W, Nb, Zn, Ta, Cr, and Ge.
[0011] Furthermore, the clay is formed by mixing 92-96% kaolin with 4-7% lithium-rich clay or 5-8% iron-rich clay.
[0012] Furthermore, the binder is a mixed binder of 85-90% silica sol and 10-15% alumina.
[0013] Furthermore, the preparation method of the modified ZMQ-1 molecular sieve is as follows:
[0014] (1) First, perform infrared steam baking on the ZMQ-1 molecular sieve; continuously spray steam on the ZMQ-1 molecular sieve to obtain the activated ZMQ-1 molecular sieve.
[0015] (2) Mix the silane coupling agent and sodium silicate, and heat them with microwave assistance to 70-80 °C, and react for 5-8 min to obtain the silylated modifier.
[0016] (3) Bubble nitrogen into the silylated modifier, and introduce the nitrogen containing the coupling agent into the activated ZMQ-1 molecular sieve. After the reaction, graft silicon-based groups onto the activated ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve.
[0017] Furthermore, step (1) is specifically as follows: First, perform infrared steam baking on the ZMQ-1 molecular sieve, control the baking temperature at 165-178 °C and the baking time at 10-20 min; continuously spray steam at 102-108 °C on the ZMQ-1 molecular sieve, and control the steam injection rate at 0.05-0.1 L / s to obtain the activated ZMQ-1 molecular sieve.
[0018] Furthermore, the preparation method of the silane coupling agent is as follows: Dissolve pentaerythritol triacrylate and tris(pentafluorophenyl)borane in toluene, stir at room temperature for 20 min to prepare a solution with a mass fraction of 15%; then slowly dropwise add triethoxysilane with the same molar mass as pentaerythritol triacrylate. After dropping, raise the temperature to 62 °C and react under negative pressure for 2 h, and finally remove the solvent.
[0019] Furthermore, step (3) is specifically as follows: Bubble nitrogen into the silylated modifier, and introduce the nitrogen containing the coupling agent into the activated ZMQ-1 molecular sieve, control the space velocity at 300-450 h -1 , control the reaction temperature at 225-316 °C, control the reaction time at 0.8-1.6 h. After the reaction, graft silicon-based groups onto the activated ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve.
[0020] To better achieve the object of the present invention, the present invention also provides a preparation method of a silicon-modified octane number promoter based on ZMQ-1 molecular sieve, comprising the following steps:
[0021] 1) Mix clay, pseudo-boehmite and binder, add water for slurrying, and control the solid content at 25-45%;
[0022] 2) Add the modified ZMQ-1 molecular sieve to the product obtained in the previous step, and mix at 45-60 °C and a stirring speed of 500-1500 r / min for 20-30 min;
[0023] 3) Spray-form and calcine the product obtained in the previous step to obtain a silicon-modified octane number promoter.
[0024] Furthermore, the average particle size of the silicon-modified octane number promoter is 200-350 μm.
[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: By performing infrared steam baking treatment on the ZMQ-1 molecular sieve, infrared baking can optimize the crystal structure of the molecular sieve, increase the number and activity of active sites, thereby improving the catalytic performance of the molecular sieve. At the same time, the binding between the particles of the molecular sieve becomes tighter, enhancing the activity and stability of the molecular sieve. High-temperature steam can make the pores of the molecular sieve more unobstructed, thereby increasing the effective adsorption sites and improving the adsorption performance. Then, through modification with silane coupling agent and sodium silicate, a silicon-modified ZMQ-1 molecular sieve is obtained. At the same time, the mixed clay is modified with metal oxide and cetyltrimethylammonium chloride to reduce the agglomeration phenomenon between clay particles, improve the dispersion performance, enhance the stability of the clay, and at the same time contribute to improving the mechanical properties. The promoter prepared by the present invention, when used in combination with the main catalyst, can increase the gasoline yield while increasing the gasoline octane number, reducing the gasoline olefin content and reducing the coke formation. Specific Embodiments
[0026] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0027] Example 1: In some embodiments, a preparation method of a silicon-modified octane number promoter based on ZMQ-1 molecular sieve comprises the following steps:
[0028] 1) Prepare a silane coupling agent:
[0029] Pentaerythritol triacrylate and tris(pentafluorophenyl)borane were dissolved in toluene and stirred at room temperature for 20 min to obtain a 15 wt% solution. Then, triethoxysilane with the same molar mass as pentaerythritol triacrylate was slowly added dropwise. After the addition, the temperature was raised to 62 °C and the reaction was carried out under negative pressure for 2 h. Finally, the solvent was removed.
[0030] 2) Preparation of modified ZMQ-1 molecular sieve:
[0031] First, the ZMQ-1 molecular sieve was baked with infrared steam, and the baking temperature was controlled at 165 °C and the baking time was controlled at 10 min. The activated ZMQ-1 molecular sieve was obtained by continuously spraying 102 °C water vapor on the ZMQ-1 molecular sieve, and the spraying rate of the steam was controlled at 0.05 L / s.
[0032] The silane coupling agent and sodium silicate were mixed and heated to 70 °C by microwave-assisted heating for 5 min to obtain a silanized modifier.
[0033] Nitrogen was bubbled into the silanized modifier, and the nitrogen containing the coupling agent was introduced into the activated ZMQ-1 molecular sieve. The space velocity was controlled at 300 h -1 , the reaction temperature was controlled at 225 °C, the reaction time was controlled at 0.8 h, and after the reaction, a silicon-based group was grafted onto the activated ZMQ-1 molecular sieve to obtain a modified ZMQ-1 molecular sieve.
[0034] 3) Preparation of clay:
[0035] 92% kaolin and 8% iron-rich clay were mixed to obtain a mixed clay, and then metal oxides and cetyltrimethylammonium chloride were added. The content of metal oxides in the mixed clay was 1% and the content of cetyltrimethylammonium chloride was 0.3%. The mixture was mixed evenly. The metal oxides contained V, Ti, and Mo elements.
[0036] 4) 5 parts of clay, 5 parts of pseudoboehmite, and 6 binders (obtained by mixing 85% silica sol and 15% alumina) were mixed, and water was added for slurrying. The solid content was controlled at 25%.
[0037] 5) 15 parts of the modified ZMQ-1 molecular sieve was added to the product obtained in the previous step, and the mixture was mixed at 45 °C and a stirring speed of 500 r / min for 20 min.
[0038] 6) The product obtained in the previous step was spray-molded and calcined to obtain a silicon-modified octane number promoter. The average particle size of the silicon-modified octane number promoter was 200 μm.
[0039] Example 2: In some embodiments, a method for preparing a silicon-modified octane number promoter based on a ZMQ-1 molecular sieve includes the following steps:
[0040] 1) Preparation of a silane coupling agent:
[0041] Pentaerythritol triacrylate and tris(pentafluorophenyl)borane were dissolved in toluene and stirred at room temperature for 20 min to obtain a solution with a mass fraction of 15%. Then, triethoxysilane with the same molar mass as pentaerythritol triacrylate was slowly added dropwise. After the addition, the temperature was raised to 62 °C and the reaction was carried out under negative pressure for 2 h. Finally, the solvent was removed.
[0042] 2) Preparation of modified ZMQ-1 molecular sieve:
[0043] First, the ZMQ-1 molecular sieve was baked with infrared steam. The baking temperature was controlled at 178 °C and the baking time was controlled at 20 min. The activated ZMQ-1 molecular sieve was obtained by continuously spraying 108 °C water vapor on the ZMQ-1 molecular sieve, and the spraying rate of the steam was controlled at 0.1 L / s.
[0044] The silane coupling agent and sodium silicate were mixed and heated to 80 °C by microwave-assisted heating for 8 min to obtain a silylated modifier.
[0045] Nitrogen was bubbled into the silylated modifier, and the nitrogen containing the coupling agent was introduced into the activated ZMQ-1 molecular sieve. The space velocity was controlled at 450 h -1 , the reaction temperature was controlled at 316 °C, the reaction time was controlled at 1.6 h, and a silicon-based group was grafted onto the activated ZMQ-1 molecular sieve after the reaction to obtain a modified ZMQ-1 molecular sieve.
[0046] 3) Preparation of clay:
[0047] 96% kaolin and 4% lithium-rich clay were mixed to obtain a mixed clay. Then, metal oxides and cetyltrimethylammonium chloride were added. The content of metal oxides in the mixed clay was 5% and the content of cetyltrimethylammonium chloride was 1%. The mixture was stirred evenly. The metal oxides contained V, Ti, and W elements.
[0048] 4) 30 parts of clay, 25 parts of pseudoboehmite, and 12 binders (obtained by mixing 90% silica sol and 10% alumina) were mixed, and water was added for pulping. The solid content was controlled at 45%.
[0049] 5) 50 parts of the modified ZMQ-1 molecular sieve were added to the product obtained in the previous step, and the mixture was stirred at 60 °C and a stirring speed of 1500 r / min for 30 min.
[0050] 6) The product obtained in the previous step was spray-molded and calcined to obtain a silicon-modified octane number promoter. The average particle size of the silicon-modified octane number promoter was 350 μm.
[0051] Example 3: In some embodiments, a method for preparing a silicon-modified octane number promoter based on ZMQ-1 molecular sieve includes the following steps:
[0052] 1) Preparation of silane coupling agent:
[0053] Dissolve pentaerythritol triacrylate and tris(pentafluorophenyl)borane in toluene, stir at room temperature for 20 min to obtain a solution with a mass fraction of 15%; then slowly add triethoxysilane with the same molar mass as pentaerythritol triacrylate. After dropping, raise the temperature to 62 °C and carry out a negative pressure reaction for 2 h. Finally, remove the solvent.
[0054] 2) Preparation of modified ZMQ-1 molecular sieve:
[0055] First, perform infrared steam baking on the ZMQ-1 molecular sieve, control the baking temperature at 168 °C and the baking time at 15 min; continuously spray 106 °C water vapor on the ZMQ-1 molecular sieve, control the steam injection rate at 0.08 L / s to obtain the activated ZMQ-1 molecular sieve;
[0056] Mix the silane coupling agent with sodium silicate, and heat it to 75 °C by microwave-assisted heating for 6 min to obtain a silylated modifier;
[0057] Introduce nitrogen gas into the silylated modifier to bubble, and introduce the nitrogen gas containing the coupling agent into the activated ZMQ-1 molecular sieve, control the space velocity at 350 h -1 , control the reaction temperature at 285 °C and the reaction time at 1 h. After the reaction, graft silicon-based groups on the activated ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve;
[0058] 3) Preparation of clay:
[0059] Mix 93% kaolin with 7% lithium-rich clay to obtain a mixed clay, then add metal oxides and cetyltrimethylammonium chloride. The content of metal oxides in the mixed clay is 3% and the content of cetyltrimethylammonium chloride is 0.5%, and mix evenly; the metal oxides contain elements V, Ti, Mo, and Nb.
[0060] 4) Mix 10 parts of clay, 15 parts of pseudo-boehmite and 11 binders (obtained by mixing 88% silica sol and 12% alumina), add water for slurrying, and control the solid content at 30%;
[0061] 5) Add 40 parts of the modified ZMQ-1 molecular sieve to the product obtained in the previous step, and mix at 48 °C and a stirring speed of 1200 r / min for 22 min;
[0062] 6) Spray-form and calcine the product obtained in the previous step to obtain a silicon-modified octane number promoter. The average particle size of the silicon-modified octane number promoter is 250 μm.
[0063] Example 4: The difference from Example 1 lies in that in step 3), the clay is prepared by the following method: 95% kaolin is mixed with 5% iron-rich clay to obtain a mixed clay, then metal oxides and cetyltrimethylammonium chloride are added, the content of metal oxides in the mixed clay is 4%, and the content of cetyltrimethylammonium chloride is 0.7%, and they are mixed evenly; the metal oxides contain V, Ti, Zn, and Cr elements.
[0064] Example 5: The difference from Example 1 lies in that in step 3), the metal oxides contain V, Ti, Ta, and Ge elements.
[0065] Comparative Example 1: The difference from Example 1 lies in that the ZMQ-1 molecular sieve is not subjected to infrared steam baking treatment.
[0066] Detection Experimental Example
[0067] The following parameters of the silicon-modified octane number promoter based on the ZMQ-1 molecular sieve prepared in Example 1 were measured: promoter attrition index: 2.0 wt% / h, specific surface area: 180 m 2 / g, bulk ratio: 0.65 g / cm 3 .
[0068] 3.6 kg of the promoters prepared in Example 1 and Comparative Example 1 were combined with 9.64 kg of the main catalyst, the reaction temperature was 500 °C, the feed rate of petrochemical waste oil was 1.9 kg / h, and the atomized water was 0.4 kg / h. The cracking performance is shown in Table 1.
[0069] Table 1 Cracking Performance Detection Results
[0070]
[0071] By subjecting the ZMQ-1 molecular sieve to infrared baking, the crystal structure of the molecular sieve can be optimized, the number and activity of active sites can be increased, thereby improving the catalytic performance of the molecular sieve. At the same time, the binding between the particles of the molecular sieve becomes tighter, enhancing the activity and stability of the molecular sieve. High-temperature steam can make the pores of the molecular sieve more unobstructed, further enhancing the catalytic activity. Then, through modification with silane coupling agent and sodium silicate, the silicon-modified ZMQ-1 molecular sieve is obtained. At the same time, the mixed clay is modified with metal oxides and cetyltrimethylammonium chloride to reduce the agglomeration phenomenon between clay particles, improve the dispersion performance, enhance the stability of the clay, and at the same time facilitate the improvement of mechanical properties. As can be seen from Table 1, when the promoter prepared by the present invention is used in combination with the main catalyst, it can achieve the improvement of gasoline yield, the increase of gasoline octane number, the reduction of gasoline olefin content, and the reduction of coke formation.
[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. Silicon-modified octane number additive based on ZMQ-1 molecular sieve, characterized in that: The invention comprises 15 to 50 parts of modified ZMQ-1 molecular sieve, 5 to 30 parts of clay, 5 to 25 parts of pseudo-boehmite and 6 to 12 parts of binder in parts by weight; wherein the modified ZMQ-1 molecular sieve is modified by sodium silicate and silane coupling agent; the clay is modified by hexadecyltrimethylammonium chloride and metal oxide, the content of metal oxide in the clay is 1 to 5%; the content of hexadecyltrimethylammonium chloride is 0.3 to 1%.
2. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 1, characterized in that: The metal oxide contains at least one metal element selected from the group consisting of V, Ti, Mo, W, Nb, Zn, Ta, Cr and Ge.
3. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 2, characterized in that: The clay is prepared by mixing 92-96% kaolin and 4-7% lithium-rich clay or 5-8% iron-rich clay.
4. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 3, characterized in that: The binder is a mixed binder of 85-90% silica sol and 10-15% alumina.
5. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 4, characterized in that: The preparation method of the modified ZMQ-1 molecular sieve is: (1) First, the ZMQ-1 molecular sieve is subjected to infrared steam baking; the ZMQ-1 molecular sieve is continuously sprayed with water vapor to obtain an activated ZMQ-1 molecular sieve; (2) mixing a silane coupling agent and sodium silicate, heating to 70-80° C. with microwave assistance, and reacting for 5-8 minutes to obtain a silanized modifier; (3) nitrogen is bubbled into the silanization modifier, and the nitrogen containing the coupling agent is bubbled into the activated ZMQ-1 molecular sieve. After the reaction, silicon-based groups are grafted onto the activated ZMQ-1 molecular sieve to obtain a modified ZMQ-1 molecular sieve.
6. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 5, characterized in that: Step (1) is specifically as follows: first, the ZMQ-1 molecular sieve is subjected to infrared steam baking, the baking temperature is controlled at 165-178° C., and the baking time is controlled at 10-20 min; the ZMQ-1 molecular sieve is continuously sprayed with 102-108° C. water vapor, and the steam spraying amount is controlled at 0.05-0.1 L / s to obtain an activated ZMQ-1 molecular sieve.
7. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 6, characterized in that: The preparation method of the silane coupling agent is as follows: pentaerythritol triacrylate and trispentafluorophenyl borane are dissolved in toluene, stirred at room temperature for 20 minutes, and a solution with a mass fraction of 15% is obtained; then triethoxysilane with the same molar mass as pentaerythritol triacrylate is slowly added dropwise, and after the addition is completed, the temperature is raised to 62° C., reacted under negative pressure for 2 hours, and finally the solvent is removed.
8. The silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 7, characterized in that: Step (3) is specifically as follows: nitrogen is bubbled into the silanization modifier, and the nitrogen containing the coupling agent is bubbled into the activated ZMQ-1 molecular sieve, and the air velocity is controlled at 300 to 450 h -1 The reaction temperature is controlled at 225-316°C, the reaction time is controlled at 0.8-1.6h, and after the reaction, silicon-based groups are grafted on the activated ZMQ-1 molecular sieve to obtain a modified ZMQ-1 molecular sieve.
9. A method for preparing a silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 8, characterized in that: The following steps are involved: 1) Mix clay, pseudo-boehmite and a binder, add water to slurry, and control the solid content to 25-45%; 2) adding the modified ZMQ-1 molecular sieve to the product obtained in the previous step, and mixing at 45-60° C. and 500-1500 r / min for 20-30 min; 3) The product obtained in the previous step is spray-formed and calcined to obtain a silicon-modified octane value additive.
10. The method for preparing a silicon-modified octane value additive based on ZMQ-1 molecular sieve according to claim 9, characterized in that: The average particle size of the silicon-modified octane value additive is between 200 and 350 μm.