A process for the production of 1-butene trimer

Abstract

The present application relates to the technical field of 1-butene oligomer preparation, and more particularly to a process for producing 1-butene trimer, i.e., dodecene. The present application provides a process for producing 1-butene trimer, which comprises: subjecting initial raw materials containing butane and 1-butene to catalytic reaction in a fixed-bed tubular reactor under the conditions of 50-100 DEG C, 1-2 MPa pressure, raw material space velocity 0.5-2 h ‑1 -1 of the fixed-bed tubular reactor containing a solid acid catalyst. The catalyst of the present application is simple to prepare, has high 1-butene trimerization selectivity, and can maintain high activity after long-time operation.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to a process for producing 1-butene trimer. Technical Background

[0002] Long-chain olefins, as key raw materials in petroleum refining and fine chemical industries, have significant industrial value in their production. Among them, dodecene, formed by the trimerization of C4 olefins, is a high-value-added fine chemical intermediate. Dodecene can be used as a raw material to derive a variety of important chemicals: for example, tert-dodecyl mercaptan, as a highly efficient chain transfer agent and molecular weight regulator, is widely used in the preparation of synthetic materials such as styrene-butadiene rubber, nitrile rubber, and ABS resin; calcium dodecylphenol vulcanizate can be used as a high-performance lubricant additive, possessing good acid neutralization, high-temperature detergency, and corrosion resistance; while dodecylphenol can be used to improve the leveling properties and curing speed of epoxy resin crystals. Therefore, developing efficient processes for the directional preparation of dodecene from low-carbon olefins has significant economic benefits and application prospects.

[0003] Currently, catalyst systems commonly used in industrial olefin polymerization reactions suffer from the following limitations: While the solid phosphoric acid catalyst developed by UOP in the US has achieved industrial application, it requires water injection to decompose the silicate phosphate and release the active components. This process easily leads to the gradual destruction of the catalyst framework structure, a decrease in mechanical strength, and a limited service life. The ZSM-5 molecular sieve catalyst used in ExxonMobil's MOGD process, although improving product isomerization selectivity through pore confinement, suffers from a microporous structure that easily induces mass transfer resistance and carbon deposition deactivation. Furthermore, its high reaction temperature and complex process limit its further promotion. In addition, while ionic liquid catalysts possess green characteristics such as low volatility and easy separation and recovery, their high cost, difficulties in heat and mass transfer in the reaction system, and large dosage requirements make them unsuitable for large-scale industrial applications. Therefore, developing a structurally stable, long-lasting, cost-effective C4 olefin trimerization catalyst system suitable for industrial-scale production is of significant practical importance. Summary of the Invention

[0004] To address the shortcomings of existing technologies, such as the easy clogging and mudding of solid phosphoric acid catalysts, the easy carbon deposition and deactivation of molecular sieve catalysts and their complex operation, and the high cost of ionic liquid catalysts, this invention provides a process for producing 1-butene trimer. It includes: drying a raw material containing butane and 1-butene, and then processing it in a fixed-bed tubular reactor at 50–100 °C, 1–2 MPa pressure, and a feed space velocity of 0.5–2 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; the solid acid catalyst is composed of a metal salt active component, an auxiliary agent, and a catalyst support; the metal salt active component is selected from one or more of nickel sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate; the total amount of the metal salt active component and the auxiliary agent accounts for 1-8% of the total mass of the solid acid catalyst; in the metal salt active component and the auxiliary agent, the molar ratio of phosphate ions to metal cations is 0-0.6.

[0005] As a preferred technical solution of the present invention, when the initial raw material is a mixture of butane and 1-butene, n-butane accounts for 48 wt% and 1-butene accounts for 52 wt%.

[0006] As a preferred embodiment of the present invention, the fixed-bed tubular reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0007] As a preferred embodiment of the present invention, the solid acid catalyst comprises a metal salt active component, an auxiliary agent, and a catalyst support; the metal salt active component is a mixture of zinc sulfate and ferric sulfate, wherein the ratio of zinc sulfate to ferric sulfate is nZn 2+ / nFe 3+ =4.

[0008] In this invention, as a preferred technical solution, the auxiliary agent is diammonium hydrogen phosphate.

[0009] In a preferred embodiment of the present invention, the molar ratio of phosphate ions to metal cations in the metal salt active ingredient and the auxiliaries is 0.3 to 0.6.

[0010] In a preferred embodiment of the present invention, the total amount of metal salt active components and diammonium hydrogen phosphate in the solid acid catalyst accounts for 3-6% of the total mass of the solid acid catalyst.

[0011] Compared with the prior art, the present invention has the following advantages:

[0012] The catalyst of this invention is simple to prepare and easy to operate; the catalyst has high activity, high stability and high selectivity for butene trimer products in the 1-butene trimerization reaction. Attached Figure Description

[0013] Figure 1 This is a process flow diagram for producing 1-butene trimer according to the present invention.

[0014] Among them, 1-N2 steel 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

[0015] The present invention will be described below through specific embodiments, but is not limited to the specific embodiments given below.

[0016] This invention provides a process for producing 1-butene trimer, comprising: drying a 1-butene initial feedstock containing butane and 1-butene, and then processing it in a fixed-bed tubular reactor at 50–100 °C, 1–2 MPa pressure, and a feed space velocity of 0.5–2 h⁻¹. -1 The catalytic reaction is carried out under the specified conditions; the fixed-bed tubular reactor contains a solid acid catalyst. The solid acid catalyst is composed of a metal salt active component, an auxiliary agent, and a catalyst support; the metal salt active component is selected from one or more of nickel sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate; the total amount of the metal salt active component and the auxiliary agent in the solid acid catalyst accounts for 1-8% of the total mass of the solid acid catalyst; the molar ratio of phosphate ions to metal cations in the metal salt active component and the auxiliary agent is 0-0.6.

[0017] This application provides a solid acid catalyst for the production of 1-butene trimer that can exist stably in a fixed-bed tubular reactor, has a long lifespan, and enables the continuous automation of the process for producing 1-butene trimer in this application.

[0018] In one embodiment, the fixed-bed tubular reactor is filled with quartz sand, catalyst, and quartz sand sequentially from top to bottom, which can reduce dead volume and facilitate normal reaction.

[0019] As a preferred technical solution of the present invention, when the initial raw materials are a mixture of butane and 1-butene, n-butane accounts for 48 wt% and 1-butene accounts for 52 wt%.

[0020] In one embodiment, the solid acid catalyst is composed of a metal salt active component, an additive, and a catalyst support; the metal salt active component is selected from one or more of nickel sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate.

[0021] Preferably, the active component of the metal salt is a mixture of zinc sulfate and ferric sulfate.

[0022] Preferably, the additive is diammonium hydrogen phosphate.

[0023] Preferably, the ratio of the metal salt active ingredient and the auxiliaries is nPO4. 3- / n(Zn 2+ +Fe 3+ The ratio of the active metal salt component to the auxiliaries is 0.3–0.6. More preferably, the ratio of the active metal salt component to the auxiliaries is nPO4. 3- / n(Zn 2+ +Fe 3+ )=0.6, where nAl 3+ / nFe 3+ =4.

[0024] In this application, the ratio of the metal salt active ingredient and the auxiliaries is nPO4. 3- / n(Zn 2+ +Fe 3+ When the ratio is 0.3 to 0.6, both the high conversion rate of 1-butene and the high selectivity of butene trimer products are guaranteed.

[0025] In one embodiment, the total amount of metal salt active components and promoters in the solid acid catalyst accounts for 1 to 8% of the total mass of the solid acid catalyst.

[0026] Preferably, the total amount of metal salt active components and promoters in the solid acid catalyst accounts for 3 to 6% of the total mass of the solid acid catalyst.

[0027] In this application, the total amount of metal salt active components and promoters in the solid acid catalyst accounts for 3-6% of the total mass of the solid acid catalyst, and the conversion rate of 1-butene and the selectivity of butene trimer products are relatively high.

[0028] The catalyst support described in this invention can be conventionally selected by those skilled in the art.

[0029] In a preferred embodiment, the catalyst support is γ-Al2O3.

[0030] γ-Al2O3, as a catalyst support, exhibits suitable acidity and surface area, high strength and good thermal stability in the process of producing 1-butene trimer in this application, making it very suitable for the preparation of solid acid catalysts in this application.

[0031] Preferably, the γ-Al₂O₃ has a particle size of 20–80 mesh and a specific surface area of ​​100–300 m². 2 The γ-Al₂O₃ has an average pore size of 2–20 nm and a total pore volume of 0.5–1.5 ml / g; more preferably, the γ-Al₂O₃ has a particle size of 20–40 mesh and a specific surface area of ​​247 m² / g. 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0032] In this application, the suitable pore size and pore volume of γ-Al2O3 not only ensure the high activity of the catalyst, but also promote the formation of 1-butene trimer in this application, resulting in high production efficiency and low synthesis cost.

[0033] In one embodiment, the process for producing 1-butene trimer includes: drying a raw material containing butane and 1-butene, and then processing it in a fixed-bed tubular reactor at 50–100 °C, 1–2 MPa pressure, and for 0.5–2 h. -1The catalytic reaction is carried out under conditions of liquid hourly space velocity; wherein the fixed-bed tubular reactor contains a solid acid catalyst.

[0034] In a preferred embodiment, the process for producing 1-butene trimer includes: pressurizing and purging N2 in N2 cylinder 1 for 20 min; drying the raw material in raw material tank 2 in drying tanks 3 and 4; and then introducing the raw material into a fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5, and heating at 100 °C for 2 h. -1 After the catalytic reaction is completed under space velocity conditions, the product is introduced into the gas-liquid separator 7 for separation and then enters the gas chromatograph 8.

[0035] 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.

[0036] In one embodiment, the method for preparing the catalyst includes the following steps:

[0037] (1) The catalyst support was calcined at 500 °C for 4 h to obtain the treated catalyst support;

[0038] (2) The treated catalyst support was immersed in an aqueous solution containing a mixture of metal salt and diammonium hydrogen phosphate active ingredients and immersed overnight at a constant temperature of 70 °C. The volume ratio of the treated catalyst support to the aqueous solution containing the mixture of metal salt and diammonium hydrogen phosphate active ingredients was 1:1.03.

[0039] (3) The solid obtained in step (2) is placed in a 110 ℃ drying oven and dried for 2 h, and then calcined at 500 ℃ for 4 h to obtain the product.

[0040] The invention will be described in more detail below by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. Unless otherwise specified, all raw materials used in the following examples are commercially available.

[0041] Example 1

[0042] Example 1 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60°C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0043] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0044] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes nickel sulfate; the total amount of nickel sulfate and the additive in the solid acid catalyst accounts for 3 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / nNi 2+ =0; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0045] The preparation method of the catalyst includes the following steps:

[0046] (1) The catalyst support was calcined at 500 °C for 4 h to obtain the treated catalyst;

[0047] (2) The treated catalyst support is immersed in an aqueous solution containing metal active components and additives and kept at a constant temperature of 70 °C overnight. The volume ratio of the treated catalyst support to the aqueous solution of the metal salt and diammonium hydrogen phosphate active components is 1:1.03.

[0048] (3) The solid obtained in step (2) is placed in an oven at 120 ℃ and dried for 2 h, and then calcined at 500 ℃ for 4 h to obtain the final product.

[0049] Example 2

[0050] Example 2 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60°C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0051] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0052] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes ferric sulfate; the total amount of ferric sulfate and the additive in the solid acid catalyst accounts for 3 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / nFe 3+ =0; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0053] The preparation method of the catalyst is the same as that in Example 1.

[0054] Example 3

[0055] Example 3 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60°C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0056] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0057] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate; the total amount of zinc sulfate and the additive in the solid acid catalyst accounts for 3 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / nZn 2+ =0; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0058] The preparation method of the catalyst is the same as that in Example 1.

[0059] Example 4

[0060] Example 4 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60°C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0061] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0062] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes aluminum sulfate; the total amount of aluminum sulfate and the additive in the solid acid catalyst accounts for 3 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / nAl 3+ =0; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0063] The preparation method of the catalyst is the same as that in Example 1.

[0064] Example 5

[0065] Example 5 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60 °C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0066] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0067] The solid acid catalyst comprises a metal salt active component, an auxiliary agent, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and auxiliary agent in the solid acid catalyst accounts for 3 wt% of the total mass of the solid acid catalyst; the auxiliary agent is diammonium hydrogen phosphate; the ratio of phosphate ions in the auxiliary agent to metal cations in the metal salt active component is nPO4. 3- / n(Zn 2+ +Fe 3+)=0, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0068] The preparation method of the catalyst is the same as that in Example 1.

[0069] Example 6

[0070] Example 6 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 5, except that the active components of the metal salt are zinc sulfate and aluminum sulfate.

[0071] The preparation method of the catalyst is the same as that in Example 1.

[0072] Example 7

[0073] Example 7 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 5, except that the active components of the metal salt are zinc sulfate and nickel sulfate.

[0074] The preparation method of the catalyst is the same as that in Example 1.

[0075] Example 8

[0076] Example 8 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60 °C and the liquid hourly space velocity (LISH) is 0.5 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0077] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0078] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and additive in the solid acid catalyst accounts for 1 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / n(Zn2+ +Fe 3+ )=0, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0079] The preparation method of the catalyst is the same as that in Example 1.

[0080] Example 9

[0081] Example 9 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 8, except that the total amount of sulfate and additives in the solid acid catalyst accounts for 5 wt% of the total mass of the solid acid catalyst.

[0082] The preparation method of the catalyst is the same as that in Example 1.

[0083] Example 10

[0084] Example 10 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 8, except that the total amount of sulfate and additives in the solid acid catalyst accounts for 8 wt% of the total mass of the solid acid catalyst.

[0085] The preparation method of the catalyst is the same as that in Example 1.

[0086] Example 11

[0087] Example 11 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 60 °C and the liquid hourly space velocity (LISH) is 1 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0088] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0089] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and additive in the solid acid catalyst accounts for 5 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / n(Zn 2+ +Fe 3+ )=0, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0090] The preparation method of the catalyst is the same as that in Example 1.

[0091] Example 12

[0092] Example 12 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 11, except that the time space velocity of the feed liquid is 2 h⁻¹. -1 .

[0093] The preparation method of the catalyst is the same as that in Example 1.

[0094] Example 13

[0095] Example 13 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 2 MPa using a dual-plunger micro-pump 5. The reactor is kept at 80 °C and the liquid hourly space velocity (LISH) is 2 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0096] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0097] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and additive in the solid acid catalyst accounts for 5 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / n(Zn2+ +Fe 3+ )=0, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0098] The preparation method of the catalyst is the same as that in Example 1.

[0099] Example 14

[0100] Example 14 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 13, except that the reaction temperature is 100°C.

[0101] The preparation method of the catalyst is the same as that in Example 1.

[0102] Example 15

[0103] Example 15 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 1 MPa using a dual-plunger micro-pump 5. The reactor is operated at 100 °C with a liquid hourly space velocity (LISH) of 2 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0104] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0105] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and additive in the solid acid catalyst accounts for 5 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / n(Zn 2+ +Fe 3+ )=0, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0106] The preparation method of the catalyst is the same as that in Example 1.

[0107] Example 16

[0108] Example 16 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is as follows: Figure 1 N2 cylinder 1 is purged with N2 for 20 min. Butane and 1-butene feedstocks in feedstock tank 2 are dried in drying tanks 3 and 4, and then introduced into fixed-bed tubular reactor 6 at a pressure of 1 MPa using a dual-plunger micro-pump 5. The reactor is operated at 100 °C with a liquid hourly space velocity (LISH) of 2 h⁻¹. -1 The catalytic reaction was carried out under certain conditions. After the reaction was completed, the product was separated by gas-liquid separator 7 and introduced into gas chromatograph 8.

[0109] The fixed-bed reactor is filled with quartz sand, catalyst and quartz sand in sequence from top to bottom.

[0110] The solid acid catalyst comprises a metal salt active component, an additive, and a catalyst support; the metal salt active component includes zinc sulfate and ferric sulfate; the total amount of sulfate and additive in the solid acid catalyst accounts for 5 wt% of the total mass of the solid acid catalyst; the additive is diammonium hydrogen phosphate; the ratio of phosphate ions in the additive to metal cations in the metal salt active component is nPO4. 3- / n(Zn 2+ +Fe 3+ )=0.3, where nZn 2+ / nFe 3+ =4; the catalyst support is γ-Al2O3 with an average specific surface area of ​​247 m². 2 / g, with an average pore size of 11 nm and a total pore volume of 0.73 ml / g.

[0111] The preparation method of the catalyst is the same as that in Example 1.

[0112] Example 17

[0113] Example 17 of the present invention provides a process for producing 1-butene trimer, the specific implementation method of which is the same as that of Example 16, except that the ratio of phosphate ions to metal cations in the auxiliary agent is nPO4. 3- / n(Zn 2+ +Fe 3+ =0.6.

[0114] The preparation method of the catalyst is the same as that in Example 1.

[0115] Performance evaluation

[0116] After the process for producing 1-butene trimer is completed, the product is separated by a gas-liquid separator and then introduced into a gas chromatograph to calculate the reaction conversion and selectivity. Specifically: the components of the raw material and tail gas are 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 is collected, it is 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 is area normalization, calculating the composition of each component in the liquid product based on the peak area of ​​each component.

[0117] Example 1 67.89 30.72 Example 2 86.79 23.37 Example 3 72.06 34.98 Example 4 58.63 17.37 Example 5 78.96 35.91 Example 6 60.21 27.66 Example 7 74.69 26.38 Example 8 67.39 31.73 Example 9 82.27 36.17 Example 10 79.93 33.18 Example 11 82.77 33.67 Example 12 83.01 33.12 Example 13 85.87 35.39 Example 14 89.58 36.42 Example 15 87.89 35.94 Example 16 92.83 36.44 Example 17 94.19 37.67

[0118] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges therein, and variations within those ranges should be interpreted as being covered by the appended claims where possible.

Claims

1. A process for producing 1-butene trimer, characterized in that: The initial feedstock containing butane and 1-butene is dried and then placed in a fixed-bed tubular reactor at 50–100 °C, 1–2 MPa pressure, and a feed space velocity of 0.5–2 h⁻¹. -1 The catalytic reaction is carried out under the following conditions; wherein the fixed-bed tubular reactor contains a solid acid catalyst; the solid acid catalyst is composed of a metal salt active component, an auxiliary agent and a catalyst support; the metal salt active component is selected from one or more of nickel sulfate, aluminum sulfate, ferric sulfate and zinc sulfate; the total amount of the metal salt active component and the auxiliary agent in the solid acid catalyst accounts for 1 to 8% of the total mass of the solid acid catalyst; the molar ratio of phosphate ions to metal cations in the metal salt active component and the auxiliary agent is 0 to 0.

6.

2. The process for producing 1-butene trimer according to claim 1, characterized in that, The fixed-bed tubular reactor is filled with quartz sand, catalyst, and quartz sand in sequence from top to bottom.

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