Solid acid catalyst for ether after C4 olefin trimer and its preparation method and application

Abstract

This invention relates to the field of catalyst technology, specifically to a solid acid catalyst for post-etherified C4 olefin trimers, its preparation method, and its application. The catalyst comprises at least a metal salt active component, diammonium hydrogen phosphate, and a catalyst support; the metal salt active component includes aluminum sulfate and ferric sulfate; the molar ratio of phosphate ions in the diammonium hydrogen phosphate to metal cations in the metal salt active component is nPO4. 3‑ / n(Al 3+ +Fe 3+ The total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst accounts for 5-10% of the total mass of the solid acid catalyst. By optimizing the formulation and process of the solid acid catalyst, the problems of easy mudding and clogging of existing solid phosphoric acid catalysts, easy carbon deposition and deactivation of molecular sieve catalysts and complex process operation, and high cost of ionic liquid catalysts are effectively solved, so as to better meet the production and application needs of post-etherified C4 olefin trimers.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a solid acid catalyst for post-etherified C4 olefin trimers, its preparation method, and its application. Background Technology

[0002] Long-chain olefins are important chemical raw materials in petroleum refining and fine chemical production. Among them, dodecene, a trimer of C4 olefins, is an important fine chemical intermediate. Tertiary dodecyl mercaptan, derived from dodecene, is mainly used as a molecular weight regulator and chain transfer agent in polymerization reactions, and is widely used in the production of polymers such as styrene-butadiene rubber, nitrile rubber, ABS resin, polyvinyl chloride, and polyethylene. It can also be used as a stabilizer and antioxidant. Calcium dodecylphenol sulfate is an excellent lubricant additive with good acid neutralization ability, high-temperature detergency, antioxidant properties, and corrosion resistance. Dodecylphenol can be used in epoxy resin crystal adhesives to improve surface leveling properties and accelerate curing speed. Therefore, developing a process for preparing dodecene from low-carbon olefins has significant economic benefits and application prospects.

[0003] Solid phosphoric acid catalysts produced by UOP (Universal Optoelectronics) in the United States are a mature and widely used type of catalyst in the industrial production of olefin complexes. These catalysts, using diatomaceous earth as a support, are prepared by impregnating a phosphoric acid solution and exhibit high activity, meeting the needs of large-scale industrial production. However, during use, water must be injected to hydrolyze the silica phosphate to generate phosphoric acid, promoting the release of the active component. However, the continuous hydrolysis of silica phosphate can damage the catalyst's framework structure, leading to a decrease in mechanical strength and severely affecting its service life. ExxonMobil's MOGD process uses ZSM-5 molecular sieves as a support, utilizing the confinement effect of its pores to selectively convert light olefins into high molecular weight isoolefins. However, the microporous structure of molecular sieves restricts the diffusion of product molecules and easily leads to carbon deposition within the pores, thus reducing catalyst activity. Simultaneously, molecular sieve catalysts require high reaction temperatures and have complex process equipment operation, limiting their industrial application. Ionic liquids are complex salts composed of organic cations and complex anions, possessing advantages such as non-toxicity, non-volatility, and ease of separation and recovery, aligning with the principles of green chemistry. For example, Chinese patent application (publication number CN119346166A) discloses ionic liquid catalysts for the synthesis of long-chain alkylbenzenes, their preparation methods, and applications, including improving reaction activity through the use of mixed multi-acidic ionic liquid catalysts. However, ionic liquid catalysts are expensive, heat and mass transfer are difficult to control during the reaction, and they require large quantities, which limits their industrial application. Summary of the Invention

[0004] To address the aforementioned issues, this invention provides a solid acid catalyst for post-etherified C4 olefin trimers, its preparation method, and its application. By optimizing the formulation and process of the solid acid catalyst, it effectively solves the problems of existing solid phosphoric acid catalysts being prone to mud formation and clogging, molecular sieve catalysts being prone to carbon deposition and deactivation and having complex process operations, and ionic liquid catalysts having high costs, thus better meeting the production and application needs of post-etherified C4 olefin trimers.

[0005] This invention provides a solid acid catalyst for post-etherified C4 olefin trimers, comprising at least a metal salt active component, diammonium hydrogen phosphate, and a catalyst support; the metal salt active component includes aluminum sulfate and ferric sulfate; the molar ratio of phosphate ions in the diammonium hydrogen phosphate to metal cations in the metal salt active component is nPO4. 3- / n(Al 3+ +Fe 3+ =0.1-0.7; the total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst accounts for 5-10% of the total mass of the solid acid catalyst.

[0006] In one embodiment, the molar ratio of phosphate ions to metal cations in the diammonium hydrogen phosphate active component nPO4 is... 3- / n(Al 3+ +Fe 3+ =0.3-0.6.

[0007] In one embodiment, the molar ratio of phosphate ions to metal cations in the diammonium hydrogen phosphate active component nPO4 is... 3- / n(Al 3+ +Fe 3+ =0.45-0.5.

[0008] In one embodiment, the total amount of the metal salt active component and diammonium hydrogen phosphate in the solid acid catalyst accounts for 7-8% of the total mass of the solid acid catalyst.

[0009] In one embodiment, the molar ratio of aluminum ions in aluminum sulfate to iron ions in ferric sulfate is nAl 3+ / nFe 3+ It is 7-8.

[0010] In one embodiment, the catalyst support comprises a γ-Al2O3 support.

[0011] In one embodiment, the specific surface area of ​​the γ-Al₂O₃ support is 100-300 m². 2 / g, with an average pore size of 2-20 nm and a total pore volume of 0.5-1.5 mL / g.

[0012] In one embodiment, the specific surface area of ​​the γ-Al₂O₃ support is 247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 mL / g.

[0013] In one embodiment, the γ-Al2O3 support is ground to a particle size of 20-80 mesh.

[0014] In one embodiment, the γ-Al2O3 support is ground to a particle size of 20-40 mesh.

[0015] This application provides a solid acid catalyst for the production of post-etherified C4 olefin trimers that can exist stably in a fixed-bed tubular reactor, has a long lifespan, and enables the continuous automation of the process for producing post-etherified C4 olefin trimers in this application.

[0016] In this application, the molar ratio of phosphate and metal cation in the active component of diammonium hydrogen phosphate (nPO4) is optimized. 3- / n(Al 3+ +Fe 3+ The concentration of 0.3-0.6, especially in the range of 0.45-0.5, ensures both high conversion rates of C4 olefins after etherification and high selectivity of butene trimer products. The reasons for this may be: aluminum sulfate and ferric sulfate form an aluminum-iron phosphate lattice structure under the action of diammonium hydrogen phosphate. The specific ratio of phosphate to metal cations (0.3-0.6) stabilizes the lattice, preventing mud formation caused by phosphate dissolution; the bimetallic synergy optimizes the distribution of acidic sites, weakening strong acid sites (reducing carbon deposition side reactions) while retaining moderately strong acid sites (promoting the main butene trimer reaction), achieving a balance between activity and stability.

[0017] In this application, by further optimizing the total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst to 5-10% of the total mass of the solid acid catalyst, the conversion rate of C4 olefins after etherification and the selectivity of butene trimer products are relatively high. Simultaneously, it effectively balances catalytic activity and long-term stability, avoiding deactivation due to insufficient activity or excessive carbon deposition. Too low an active component content (<5%) leads to insufficient acidic site density and a low reaction rate; too high a content (>10%) covers the support pores, increases the density of strong acid sites, and accelerates carbon deposition. By controlling it within the range of 5-10%, especially within the range of 7-8%, the active site density and support pore structure are optimized, ensuring sufficient contact of reactants while avoiding pore blockage and extending catalyst life.

[0018] In this application, by using γ-Al2O3 support as catalyst support, its pore size and pore volume are further controlled, ensuring the high activity of the solid acid catalyst, promoting the formation of the post-etherified C4 olefin trimer in this application, resulting in high production efficiency and low synthesis cost.

[0019] The catalyst of this invention is simple to prepare and easy to operate. The catalyst has high activity, high stability and high butene trimer selectivity in the post-etherification of C4 olefin trimerization.

[0020] Another aspect of the present invention provides a method for preparing a solid acid catalyst for post-etherified C4 olefin trimer, comprising the following steps: calcining a catalyst support at 500-600°C for 3-4 hours to obtain a pretreated catalyst support; adding a metal salt active component, diammonium hydrogen phosphate, to water to prepare an aqueous solution of the active component; immersing the pretreated catalyst support in the aqueous solution of the active component at a constant temperature of 70-80°C overnight; drying the separated solid in an oven at 110-120°C for 2-3 hours, and calcining it at 400-500°C for 4-5 hours.

[0021] In one embodiment, the volume ratio of the pretreated catalyst support to the aqueous solution of the active ingredient is 1:0.9-1.1.

[0022] In one embodiment, the volume ratio of the pretreated catalyst support to the aqueous solution of the active ingredient is 1:1.03.

[0023] Another aspect of the present invention provides an application of a solid acid catalyst for the preparation of post-etherified C4 olefin trimers.

[0024] In one embodiment, the preparation process of the post-etherified carbotetraolefin trimer includes the following steps:

[0025] After drying, the raw materials butane, 1-butene, cis-2-butene, and / or trans-2-butene are subjected to a fixed-bed tubular reactor at 50-100℃, 2-4 MPa, and a feed space velocity of 0.5-4 h⁻¹. - The catalytic reaction is carried out under the following conditions: ¹; the fixed-bed tubular reactor is filled with a solid acid catalyst.

[0026] The space velocity mentioned in this invention refers to the amount of material processed per unit reaction volume per unit time, and the unit is the reciprocal of time.

[0027] In one embodiment, the fixed-bed tubular reactor is filled with quartz sand, solid acid catalyst and quartz sand in sequence from top to bottom.

[0028] This invention optimizes the filling of a fixed-bed tubular reactor with quartz sand, solid acid catalyst, and quartz sand sequentially from top to bottom. By controlling the temperature, pressure, and space velocity of the catalytic reaction, it eliminates local overheating and fluid inhomogeneity, synergistically inhibits carbon deposition, reduces side reactions (such as cracking and dimerization), ensures sufficient conversion rate, and extends the reactor's operating cycle.

[0029] Beneficial effects

[0030] 1. This invention provides a solid acid catalyst for post-etherified C4 olefin trimers, its preparation method, and its application. By optimizing the formulation and process of the solid acid catalyst, it effectively solves the problems of existing solid phosphoric acid catalysts being prone to mud formation and clogging, molecular sieve catalysts being prone to carbon deposition and deactivation and having complex process operation, and ionic liquid catalysts having high cost, thus better meeting the production and application needs of post-etherified C4 olefin trimers.

[0031] 2. The solid acid catalyst provided in this application for the production of post-etherified C4 olefin trimers can exist stably in a fixed-bed tubular reactor, has a long lifespan, and enables the continuous automation of the process for producing post-etherified C4 olefin trimers in this application.

[0032] 3. In this application, the molar ratio of phosphate and metal cation in the active component of diammonium hydrogen phosphate (nPO4) is optimized. 3- / n(Al 3+ +Fe 3+ The concentration of 0.3-0.6, especially in the range of 0.45-0.5, ensures both high conversion rates of the etherified C4 olefins and high selectivity of the butene trimer.

[0033] 4. In this application, by further optimizing the total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst to account for 5-10% of the total mass of the solid acid catalyst, the conversion rate of C4 olefins after etherification and the selectivity of butene trimer products are relatively high. At the same time, the catalytic activity and long-term stability are effectively balanced, and deactivation caused by insufficient activity or excessive carbon deposition is avoided.

[0034] 5. This invention optimizes the fixed-bed tubular reactor by sequentially filling it with quartz sand, solid acid catalyst, and quartz sand from top to bottom. Combined with the control of catalytic reaction temperature, pressure, and space velocity, it eliminates local overheating and fluid unevenness, synergistically inhibits carbon deposition, reduces side reactions (such as cracking and dimerization), ensures sufficient conversion rate, and extends the reactor operating cycle. Attached Figure Description

[0035] Figure 1 The process flow diagram for the preparation of post-etherified C4 olefin trimer provided for the application examples is as follows: 1-N2 cylinder; 2-raw material tank; 3-drying tank 1; 4-drying tank 2; 5-dual plunger micro pump; 6-fixed bed tubular reactor; 7-gas-liquid separator; 8-gas chromatograph. Detailed Implementation

[0036] Example 1

[0037] Example 1 of the present invention provides a solid acid catalyst for post-etherified C4 olefin trimers, comprising a metal salt active component, diammonium hydrogen phosphate, and a catalyst support; the metal salt active component comprises aluminum sulfate and ferric sulfate; the molar ratio of phosphate ions in the diammonium hydrogen phosphate to metal cations in the metal salt active component is nPO4. 3- / n(Al 3+ +Fe 3+ =0.45; The total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst accounts for 7% of the total mass of the solid acid catalyst.

[0038] The molar ratio of aluminum ions to ferric ions in aluminum sulfate (nAl) 3+ / nFe 3+ It is 8.

[0039] The catalyst support is a γ-Al₂O₃ support with a specific surface area of ​​247 m². 2 The sample was 0.73 mL / g, with an average pore size of 11 nm and a total pore volume of 0.73 mL / g, and was sourced from commercially available products.

[0040] The γ-Al2O3 support is ground to a particle size of 20-40 mesh.

[0041] Example 1 of the present invention provides a method for preparing a solid acid catalyst for post-etherified C4 olefin trimer, comprising the following steps: calcining a catalyst support at 500°C for 4 hours to obtain a pretreated catalyst support; adding a metal salt active component, diammonium hydrogen phosphate, to water to prepare an aqueous solution of the active component; immersing the pretreated catalyst support in the aqueous solution of the active component at a constant temperature of 70°C overnight; and drying the separated solid in an oven at 120°C for 2 hours, followed by calcination at 500°C for 4 hours.

[0042] The volume ratio of the pretreated catalyst support to the aqueous solution of the active ingredient is 1:1.03.

[0043] Example 2

[0044] Example 2 of the present invention provides a solid acid catalyst for post-etherified C4 olefin trimers and its preparation method. The specific implementation method is the same as that in Example 1, except that the molar ratio of phosphate ions to metal cations in the diammonium hydrogen phosphate active component is nPO4. 3- / n(Al 3+ +Fe 3+ =0.18; The total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0045] Example 3

[0046] Example 3 of the present invention provides a solid acid catalyst for post-etherified C4 olefin trimer and its preparation method. The specific implementation method is the same as that of Example 1, except that the total amount of metal salt active component and diammonium hydrogen phosphate in the solid acid catalyst accounts for 10% of the total mass of the solid acid catalyst.

[0047] Comparative Example 1

[0048] Comparative Example 1 of the present invention provides a solid acid catalyst for post-etherified C4T olefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified C4T olefin trimers includes a metal salt active component and a catalyst support, wherein the metal salt active component is replaced with nickel sulfate. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0049] Comparative Example 2

[0050] Comparative Example 2 of the present invention provides a solid acid catalyst for post-etherified C4T olefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified C4T olefin trimers includes a metal salt active component and a catalyst support, wherein the metal salt active component is replaced with aluminum sulfate. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0051] Comparative Example 3

[0052] Comparative Example 3 of the present invention provides a solid acid catalyst for post-etherified C4T olefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified C4T olefin trimers includes a metal salt active component and a catalyst support, wherein the metal salt active component is replaced with ferric sulfate. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0053] Comparative Example 4

[0054] Comparative Example 4 of the present invention provides a solid acid catalyst for post-etherified carbotetraolefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified carbotetraolefin trimers includes a metal salt active component and a catalyst support, wherein the metal salt active component is replaced with zinc sulfate. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0055] Comparative Example 5

[0056] Comparative Example 5 of the present invention provides a solid acid catalyst for post-etherified carbotetraolefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified carbotetraolefin trimers includes a metal salt active component and a catalyst support. The metal salt active component is replaced by a combination of aluminum sulfate and nickel sulfate. The molar ratio of aluminum ions in aluminum sulfate to nickel ions in nickel sulfate is nAl 3+ / nNi 2+ The value is 8. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0057] Comparative Example 6

[0058] Comparative Example 6 of the present invention provides a solid acid catalyst for post-etherified carbotetraolefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified carbotetraolefin trimers includes a metal salt active component and a catalyst support. The metal salt active component is replaced by a combination of aluminum sulfate and nickel sulfate. The molar ratio of aluminum ions in aluminum sulfate to zinc ions in zinc sulfate is nAl 3+ / nZn 2+ The value is 8. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0059] Comparative Example 7

[0060] Comparative Example 7 of the present invention provides a solid acid catalyst for post-etherified carbotetraolefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified carbotetraolefin trimers includes a metal salt active component and a catalyst support. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0061] Comparative Example 8

[0062] Comparative Example 8 of the present invention provides a solid acid catalyst for post-etherified carbotetraolefin trimers and its preparation method. The specific implementation method is the same as in Example 1, except that the solid acid catalyst for post-etherified carbotetraolefin trimers includes a metal salt active component and a catalyst support. The metal salt active component is replaced by a combination of ferric sulfate and nickel sulfate. The molar ratio of iron ions in the ferric sulfate to nickel ions in the nickel sulfate is nFe 3+ / nNi 2+ The value is 8. The metal salt active component in the solid acid catalyst accounts for 5% of the total mass of the solid acid catalyst.

[0063] Application Example 1

[0064] Application Example 1 of the present invention provides a process for preparing post-etherified C4 olefin trimers, comprising the following steps:

[0065] See Figure 1 After purging N2 from cylinder 1 for 20 min, the raw materials 48wt% butane, 34wt% 1-butene, and 18wt% cis-2-butene from raw material tank 2 are dried in drying tanks 3 and 4. Then, they are introduced into a fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is then heated at 100°C with a raw material space velocity of 2 h⁻¹. - The catalytic reaction was carried out under the conditions of ¹. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8 to calculate the reaction conversion rate and selectivity. The fixed-bed tubular reactor was filled with a solid acid catalyst (Example 1). The fixed-bed tubular reactor was filled with quartz sand, solid acid catalyst and quartz sand in sequence from top to bottom.

[0066] Application Example 2

[0067] Application Example 2 of the present invention provides a preparation process for post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Application Example 1, except that the solid acid catalyst (Example 1) is replaced by a solid acid catalyst (Example 2).

[0068] Application Example 3

[0069] Application Example 3 of the present invention provides a preparation process for post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Application Example 1, except that the solid acid catalyst (Example 1) is replaced by a solid acid catalyst (Example 3).

[0070] Application Example 4

[0071] Application Example 4 of the present invention provides a preparation process for post-etherified C4 olefin trimer. The specific implementation method is the same as that of Application Example 1, except that the raw materials in the raw material tank 2 are replaced with 48wt% butane, 34wt% 1-butene, and 18wt% trans-2-butene.

[0072] Application Example 5

[0073] Application Example 5 of the present invention provides a preparation process for post-etherified C4 olefin trimer. The specific implementation method is the same as that of Application Example 1, except that the raw materials in the raw material tank 2 are replaced with 48wt% butane, 34wt% 1-butene, 12wt% cis-2-butene, and 6wt% trans-2-butene.

[0074] Application Comparative Example 1

[0075] Comparative Example 1 of the present invention provides a process for preparing post-etherified carbotetraolefin trimers, comprising the following steps:

[0076] See Figure 1After purging N2 from cylinder 1 for 20 minutes, the raw materials butane, 1-butene, and cis-2-butene from raw material tank 2 are dried in drying tanks 3 and 4. Then, they are introduced into a fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is then heated at 70°C with a raw material space velocity of 1 h⁻¹. - The catalytic reaction was carried out under the conditions of ¹. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8 to calculate the reaction conversion rate and selectivity. The fixed-bed tubular reactor was filled with a solid acid catalyst (Comparative Example 1). The fixed-bed tubular reactor was filled with quartz sand, solid acid catalyst and quartz sand in sequence from top to bottom.

[0077] Application Comparative Example 2

[0078] Comparative Example 2 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 2).

[0079] Application Comparative Example 3

[0080] Comparative Example 3 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 3).

[0081] Application Comparative Example 4

[0082] Comparative Example 4 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 4).

[0083] Application Comparative Example 5

[0084] Comparative Example 5 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 5).

[0085] Application Comparative Example 6

[0086] Comparative Example 6 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 6).

[0087] Application Comparative Example 7

[0088] Comparative Example 7 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 7).

[0089] Application Comparative Example 8

[0090] Comparative Example 8 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that the solid acid catalyst (Comparative Example 1) is replaced by a solid acid catalyst (Comparative Example 8).

[0091] Application Comparison Example 9

[0092] Application Comparative Example 9 of the present invention provides a preparation process for post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Application Comparative Example 1, except that the temperature of the catalytic reaction is replaced by 50°C instead of 70°C.

[0093] Application Comparison Example 10

[0094] Application Comparative Example 10 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as Application Comparative Example 1, except that the temperature of the catalytic reaction is replaced by 100°C instead of 70°C.

[0095] Application Comparative Example 11

[0096] Comparative Example 11 of the present invention provides a process for preparing post-etherified C4 olefin trimers, the specific implementation of which is the same as that of Comparative Example 1, except that the raw material space velocity is changed from 1 h⁻¹ to 1 h⁻¹. - ¹Replace with 2h - ¹.

[0097] Application Comparative Example 12

[0098] Comparative Example 12 of this invention provides a process for preparing post-etherified C4 olefin trimers, the specific implementation of which is the same as that of Comparative Example 1, except that the raw material space velocity is changed from 1 h⁻¹ to 1 h⁻¹. - ¹Replace with 4h - ¹.

[0099] Application Comparative Example 13

[0100] Comparative Example 13 of the present invention provides a process for preparing post-etherified C4 olefin trimer, the specific implementation of which is the same as that of Comparative Example 1, except that a dual-plunger micro-pump 5 is used to introduce the material into a fixed-bed tubular reactor 6 at a pressure of 4 MPa.

[0101] Performance testing

[0102] After the processes in the application examples and comparative examples were completed, the products were separated by a gas-liquid separator and then introduced into a gas chromatograph to calculate the reaction conversion rate and selectivity. Specifically, the components of the raw materials and tail gas were analyzed using a GC7900 chromatograph with an HT-PLO column, an FID detector, a vaporization chamber of 80 °C, a detector of 200 °C, and a column temperature program of initial 80 °C, hold for 5 min, then ramp to 110 °C at a rate of 5 °C / min and hold for 1 min. After the reaction liquid was collected, it was analyzed using an Agilent-6890 chromatograph with an HP-5 column, an FID detector, a vaporization chamber of 280 °C, a detection chamber of 280 °C, an initial column temperature of 60 °C held for 10 min, then ramped to 280 °C at a rate of 10 °C / min and held for 1 min. The processing method was area normalization, calculating the composition of each component in the liquid product based on the peak area of ​​each component. The results are shown in Table 1.

[0103] Table 1

[0104]

[0105] Analysis of the data in Table 1 shows that the solid acid catalysts provided in Examples 1-3, used in Examples 1-5 of this invention, combined with process control, simultaneously ensure high 1-butene conversion, high 2-butene conversion, and high dodecene selectivity.

Claims

1. A solid acid catalyst for the trimerization of post-etherified C4 olefins, characterized in that, The preparation method of the solid acid catalyst for the trimerization of post-etherified C4 olefins includes the following steps: calcining the catalyst support at 500-600℃ for 3-4 hours to obtain a pretreated catalyst support; adding the metal salt active component, diammonium hydrogen phosphate, to water to prepare an aqueous solution of the active component; immersing the pretreated catalyst support in the aqueous solution of the active component at a constant temperature of 70-80℃ overnight; drying the separated solid in an oven at 110-120℃ for 2-3 hours, and calcining it at 400-500℃ for 4-5 hours to obtain the solid acid catalyst. The active components of the metal salt include aluminum sulfate and ferric sulfate; The molar ratio of phosphate and metal cation in the active component of diammonium hydrogen phosphate (nPO4) 3- / n(Al 3+ +Fe 3 + =0.3-0.6; the total amount of metal salt active components and diammonium hydrogen phosphate accounts for 7-8% of the total mass of the solid acid catalyst; the molar ratio of aluminum ions in aluminum sulfate to iron ions in ferric sulfate is nAl 3+ / nFe 3+ The particle size is 7-8; the catalyst support comprises γ-Al₂O₃; the particle size of the γ-Al₂O₃ is 20-80 mesh, and the specific surface area is 100-300 m². 2 / g, with an average pore size of 2-20 nm and a total pore volume of 0.5-1.5 mL / g.

2. A method for preparing a solid acid catalyst for the trimerization of post-etherified C4 olefins according to claim 1, characterized in that, The process includes the following steps: calcining the catalyst support at 500-600℃ for 3-4 hours to obtain a pretreated catalyst support; A metal salt active component, diammonium hydrogen phosphate, is added to water to prepare an aqueous solution of the active component; the pretreated catalyst support is immersed in the aqueous solution of the active component and kept at a constant temperature of 70-80℃ overnight; the separated solid is placed in an oven at 110-120℃ and dried for 2-3 hours, and then calcined at 400-500℃ for 4-5 hours to obtain the solid acid catalyst; the metal salt active component includes aluminum sulfate and ferric sulfate; The molar ratio of phosphate and metal cation in the active component of diammonium hydrogen phosphate (nPO4) 3- / n(Al 3+ +Fe 3 + =0.3-0.6; the total amount of metal salt active components and diammonium hydrogen phosphate accounts for 7-8% of the total mass of the solid acid catalyst; the molar ratio of aluminum ions in aluminum sulfate to iron ions in ferric sulfate is nAl 3+ / nFe 3+ The particle size is 7-8; the catalyst support comprises γ-Al₂O₃; the particle size of the γ-Al₂O₃ is 20-80 mesh, and the specific surface area is 100-300 m². 2 / g, with an average pore size of 2-20 nm and a total pore volume of 0.5-1.5 mL / g.

3. An application of the solid acid catalyst for the trimerization of post-etherified C4 olefins according to claim 1, characterized in that, Used for the preparation of post-etherified C4 olefin trimers by post-etherification C4 olefin trimer reaction.

4. The application of the solid acid catalyst for trimerization of post-etherified C4 olefins according to claim 3, characterized in that, The preparation method of the etherified C4 olefin trimer includes the following steps: The feedstock, butane, 1-butene, and one or two selected from cis-2-butene and trans-2-butene, are dried and then placed in a fixed-bed tubular reactor at 50-100°C, 2-4 MPa, and a feed volume hourly space velocity of 0.5-4 h⁻¹. -1 The catalytic reaction is carried out under the specified conditions; the fixed-bed tubular reactor is filled with the solid acid catalyst.

5. The application of the solid acid catalyst for the trimerization of post-etherified C4-olefins according to claim 4, characterized in that, The fixed-bed tubular reactor is filled with quartz sand, solid acid catalyst and quartz sand in sequence from top to bottom.

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