A hydrogenation isomerization supported catalyst, a preparation method and a method for hydrogenation isomerization of carbon four olefins

Abstract

The application provides a hydrogen isomerization supported catalyst, a preparation method and a method for hydrogen isomerization of carbon four olefins. The hydrogen isomerization supported catalyst comprises a carrier, an active component and an additive; the carrier is at least one of a metal oxide and activated carbon; the active component comprises a metal element; the metal element is preferably at least one of iron, copper, nickel, cobalt and palladium; and the mass of the active component accounts for 0.01-20wt% of the total mass of the catalyst. The prepared catalyst can be used in catalysis of MTO carbon four olefins with high content of aldehyde ketone oxygen-containing compounds, is not inhibited by the oxygen-containing compounds, can maintain high activity of the catalyst, and can maintain high isomerization rate of 1-butene and high conversion rate of butadiene.

Description

Technical Field

[0001] This invention relates to the field of olefin hydroisomerization technology, and more specifically, to a hydroisomerization supported catalyst, a preparation method, and a method for hydroisomerization of C4 olefins. Background Technology

[0002] C4 fractions typically refer to a mixture of hydrocarbons containing four carbon atoms, primarily composed of 1-butene, 2-butene, isobutene, butadiene, isobutane, and n-butane, along with small amounts of oxygen-containing compounds. C4 fractions are byproducts of industrial production processes such as refinery catalytic cracking, steam cracking to ethylene, and methanol-to-olefins (MTO). However, the C4 composition varies significantly among these processes. Refinery catalytic cracking produces C4 fractions with high alkanes and butene content and very low butadiene content; cracked C4 fractions are mainly composed of olefins (butadiene, n-butene, and isobutene) with low alkanes content; while MTO fractions have higher 1-butene and 2-butene content, lower alkanes content, and contain mainly oxygen-containing compounds such as aldehydes and ketones.

[0003] In recent years, with the continuous expansion of production capacity in methanol-to-olefins (MTO) and methanol-to-propylene (MTP) plants, the amount of by-product C4 fractions has also increased. Therefore, how to improve the value-added utilization of by-product C4 fractions and create greater value for enterprises has become a research hotspot. The isomerization of the double bonds of 1-butene and 2-butene is one important technical route. High-purity 1-butene, as a comonomer of linear low-density polyethylene, has significant economic value. Therefore, 1-butene can be isomerized to 2-butene through a C4 hydroisomerization reaction, and then separated by distillation using 2-butene and isobutene. Finally, 2-butene can be isomerized to obtain high-purity 1-butene. This route has been proven to be a feasible path for the application of C4 olefins in industry.

[0004] The proportion of C4 hydroisomerization technology in the overall process of comprehensive utilization of C4 hydrocarbons is increasing. The SHP process of UOP in the United States (Oil Gas J, 1988, 86(49): 40-43) uses a noble metal catalyst. Although the conversion rate of butadiene reaches 99.8% and the isomerization rate of 1-butene reaches 76.1%, the increase of n-butane is too large, at 35.7%. The selective hydrogenation Pd-based catalyst developed by Qilu Petrochemical Research Institute has a butadiene conversion rate of more than 96%, a single olefin yield of more than 100%, and a 1-butene isomerization rate of more than 60%. Wells studied the isomerization activity of Ni and different noble metals supported on different alumina supports (J. Catal., 1967, 9: 70-75) and found that, except for platinum, the isomerization activity of nickel and second transition metals is better than that of third transition metal catalysts. At the same time, Al2O3 support has a promoting effect on metal isomerization activity.

[0005] The C4 hydroisomerization reaction can remove trace amounts of butadiene from the C4 feedstock and isomerize 1-butene into 2-butene. However, the current MTO process produces C4 feedstock with high levels of aldehydes and ketones (>200 ppm), which can significantly inhibit the activity of existing hydroisomerization catalysts, leading to a decrease in 1-butene isomerization rate and butadiene conversion rate.

[0006] Therefore, it is necessary to study a catalyst that can tolerate oxygen-containing compounds, improve the activity of hydroisomerization reaction in C4 by-products of MTO, and enable direct hydrogenation treatment of C4 materials with high content of aldehydes and ketones. Summary of the Invention

[0007] To address the technical problems existing in the prior art, the present invention provides a hydroisomerized supported catalyst, a preparation method, and a method for hydroisomerization of C4 olefins.

[0008] The hydroisomer supported catalyst prepared by this invention can maintain high activity and high 1-butene isomerization rate and butadiene conversion rate when catalyzing MTO C4 olefins with high content of aldehydes and ketones and oxygen-containing compounds, without being inhibited by oxygen-containing compounds. This solves the problem of efficient utilization of MTO C4 olefin resources and produces high-purity 1-butene and 2-butene.

[0009] One of the objectives of this invention is to provide a hydroisomer supported catalyst.

[0010] The hydroisomer supported catalyst includes a support, an active component, and an additive; the support is at least one of oxide and activated carbon; the active component includes a metal element; the metal element is preferably at least one of iron, copper, nickel, cobalt, and palladium; the active component accounts for 0.01 to 20 wt% of the total mass of the catalyst based on the mass of the metal element therein.

[0011] In a preferred embodiment of the present invention,

[0012] The oxide is at least one of a metal oxide and silicon dioxide; the metal oxide is preferably at least one of aluminum oxide, manganese oxide, zinc oxide, and calcium oxide.

[0013] The additive is boron. Unlike existing technologies where boron is typically used to modify metal oxide supports, in this invention, boron is loaded onto the catalyst after the active component is supported on the support to form a catalyst precursor. It acts on the active metal element after the support is loaded. Impregnating the catalyst with boron as an additive can change the chemical state of the metal element in the active component. For example, potassium borohydride acting on the active component Ni can change the electronic state of Ni, thereby enhancing the adsorption of the reactive site Ni on the raw material 1-butene and inhibiting the adsorption of oxygen-containing compounds, thus improving the hydroisomerization activity and the selective hydrogenation activity of 1,3-butadiene.

[0014] The active component, based on the mass of the metal element therein, accounts for 0.5% to 16% of the total mass of the catalyst.

[0015] The additive, calculated as boron, has a molar ratio of 0.3 to 10 with the metal element, preferably 0.5 to 4.

[0016] The support comprises 50.0% to 99.9% of the total mass of the catalyst, preferably 75.0% to 99.5%.

[0017] The precursor of the metal element in the active component is a salt of the metal element, preferably at least one of nitrate, chloride, acetate, sulfate, and carbonate.

[0018] In a preferred embodiment of the present invention,

[0019] The precursor of boron is at least one selected from borohydride, borane, boric acid and its salts; the borohydride is preferably an alkali metal borohydride, more preferably at least one selected from potassium borohydride and sodium borohydride.

[0020] The second objective of this invention is to provide a method for preparing a hydroisomer supported catalyst, comprising the steps of first loading the metal element onto a support to obtain a catalyst precursor, and then loading the promoter onto the catalyst precursor to obtain the catalyst of this invention.

[0021] Specifically, it includes the following steps:

[0022] (1) The support is mixed evenly with the aqueous solution of the precursor of the metal element, and the catalyst precursor is obtained after dehydration and drying.

[0023] (2) The catalyst precursor obtained in step (1) is added to the precursor aqueous solution of the auxiliary agent, mixed evenly, and then washed and dried to obtain the hydroisolated supported catalyst.

[0024] In a preferred embodiment of the present invention,

[0025] Step (1),

[0026] The concentration of the aqueous solution of the metal element precursor is 0.1–15 wt%, preferably 0.2–14 wt%.

[0027] The concentration of the precursor aqueous solution of the auxiliary agent is 0.1-60 wt%, preferably 1-50 wt%;

[0028] The precursor aqueous solution of the auxiliary is a boron precursor aqueous solution, wherein the molar ratio of boron to the metal element is 0.3 to 20, preferably 1 to 8. During the preparation of the catalyst, the boron precursor aqueous solution is added, and a chemical reaction occurs during the impregnation process. About half of the boron element combines with the catalyst, while the other half of the boron element remains in the solution in the form of a soluble salt. Therefore, the amount of boron in the catalyst is half the boron content in the added boron precursor aqueous solution.

[0029] The mixing time is 0.1 to 12 hours, preferably 1 to 3 hours;

[0030] The drying temperature is 60–120℃;

[0031] The drying time is 6 to 10 hours, preferably 6 to 8 hours.

[0032] In a preferred embodiment of the present invention,

[0033] Step (2),

[0034] Stir until the solution no longer produces bubbles during mixing; and / or,

[0035] Wash with deionized water; and / or,

[0036] The drying temperature is 60–120°C, preferably 60–80°C; and / or,

[0037] The drying time is 4 to 8 hours.

[0038] A third objective of this invention is to provide a hydroisomer supported catalyst prepared by the above-described method.

[0039] The fourth objective of this invention is to provide a method for preparing 1-butene or 2-butene by hydroisomerization of C4 olefins using a hydroisomerization supported catalyst, comprising the following steps:

[0040] a) Hydroisomerization unit, using the hydroisomerization supported catalyst, selectively hydrogenates 1,3-butadiene in C4 olefins to 1-butene while isomerizing 1-butene to 2-butene via hydroisomerization.

[0041] Optionally, b) the isomerization unit isomerizes 2-butene to 1-butene;

[0042] Optionally, c) selects a hydrogenation unit to selectively hydrogenate 1,3-butadiene to 1-butene.

[0043] The hydroisomerization supported catalyst prepared in this invention is used in step a) to simultaneously achieve the selective hydrogenation of 1,3-butadiene to 1-butene and the isomerization of 1-butene to 2-butene, with the two reactions occurring concurrently. Steps b) and c) are the isomerization unit for isomerizing 2-butene to 1-butene and the selective hydrogenation unit for selectively hydrogenating 1,3-butadiene to 1-butene, respectively. Depending on the specific production process requirements, these may exist in the process of preparing 1-butene or 2-butene from hydroisomerized C4 olefins. In such cases, the hydroisomerization supported catalyst of this invention is not used, but can be used as part of the overall hydroisomerization process as needed.

[0044] In a preferred embodiment of the present invention,

[0045] The C4 olefin is a C4 olefin containing an oxygen-containing compound; the oxygen-containing compound is at least one of aldehydes, ketones, or other oxygen-containing compounds; the C4 olefin is preferably a C4 byproduct obtained from a methanol-to-olefins process.

[0046] The oxygen-containing compound content in the C4 olefin is above 200 ppm.

[0047] In a preferred embodiment of the present invention,

[0048] Step a),

[0049] After the hydroisomer supported catalyst is packed into a fixed bed, it is reduced by hydrogen gas at a temperature of 400-600℃ and a pressure of 0.1-1.0MPa for 4-8 hours.

[0050] The reaction temperature of the hydroisomer unit is 30–100°C, preferably 40–70°C; the reaction pressure is 0.1–5 MPa, preferably 0.4–2.5 MPa; and the volume hourly space velocity is 0.1–10 h⁻¹. -1 Preferably 0.8 to 2 hours -1 .

[0051] The fifth objective of this invention is to provide 1-butene or 2-butene prepared from C4 olefins using hydroisomerization.

[0052] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0053] The catalyst of this invention can catalyze the hydrogenation of 1,3-butadiene to 1-butene, and at the same time catalyze the production of 2-butene from 1-butene, achieving the catalytic effect of two reactions. It has high catalytic activity and can produce high-purity 1-butene and 2-butene.

[0054] Existing C4 hydroisomer catalysts inhibit catalyst activity when catalyzing MTO by-product C4 because the MTO by-product C4 contains high levels of oxygen-containing compounds. The hydroisomer catalyst prepared in this invention can overcome the inhibition of catalyst activity by oxygen-containing compounds, achieving efficient utilization of MTO by-product C4, improving its production capacity utilization rate, and possessing high industrial application and economic value. Attached Figure Description

[0055] Figure 1 The X-ray photoelectron spectroscopy (XPS) spectra of Examples 2-4 and Comparative Example 2 are shown below.

[0056] In the figure, Ni represents Comparative Example 2, NiB represents Example 2, NiB3 represents Example 3, and NiB6 represents Example 4. The horizontal axis in the figure represents the binding energy (Ev) value, and the vertical axis represents the intensity of the diffraction peak signal value. Detailed Implementation

[0057] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0058] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0059] Test method:

[0060] X-ray photoelectron spectroscopy (XPS): Ni element was determined using a Perkin Elmer PHI 5000C X-ray photoelectron spectrometer. The test conditions were: Mg target (hv = 1263.6 eV), high voltage 14.0 kV, power 300 W, and energy 93.6 eV.

[0061] In the embodiments and comparative examples of the present invention:

[0062] 1-Butene conversion rate = (1-Butene content in raw material - 1-Butene content in product) / 1-Butene content in raw material;

[0063] 2-Butene selectivity = (2-Butene content in product – 2-Butene content in raw material) / (1-Butene content in raw material – 1-Butene content in product + 1,3-Butadiene content in raw material – 1,3-Butadiene content in product);

[0064] 1,3-Butadiene conversion rate = (1,3-Butadiene content in feedstock - 1,3-Butadiene content in product) / 1,3-Butadiene content in feedstock

[0065] Butane increment = Butane content per unit product - Butane content per unit raw material.

[0066] Example 1

[0067] 1. Catalyst Preparation

[0068] Palladium chloride was prepared into an aqueous solution of chloropalladium acid (0.2 wt% palladium). 30 g of alumina support was mixed with 50 g of the aqueous solution of chloropalladium acid for 1 h, dried at 110 °C for 6 h, and then immersed in 30 g of potassium borohydride aqueous solution (1.1 wt%). The solution was stirred slowly until no more bubbles were generated. After washing several times with deionized water and drying at 60 °C for 8 h, the PdB catalyst was obtained. The molar ratio of B to Pd in ​​the PdB catalyst was approximately 3.2.

[0069] 2. Catalyst Evaluation

[0070] In a fixed bed, the PdB catalyst prepared above was reduced by hydrogen gas at atmospheric pressure and 450°C for 6 h. Using C4 olefins from the MTO process with aldehydes and ketones containing 200 ppm of oxygen as feedstock, the reaction temperature was 45°C, the reaction pressure was 0.6 MPa, and the volume hourly space velocity was 2.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0071] Example 2

[0072] 1. Catalyst Preparation

[0073] Nickel nitrate was prepared into a nickel-ammonium solution (13.8 wt% nickel). 30 g of alumina support was mixed with 42 g of the nickel-ammonium solution for 1 h, and dried at 60 °C and 100 °C for 4 h respectively. Then, the solution was immersed in 20 g of potassium borohydride aqueous solution (25 wt%) and stirred slowly until no more bubbles were generated. The solution was washed several times with deionized water and dried at 80 °C for 4 h to obtain the NiB catalyst, where the molar ratio of B to Ni was approximately 0.51. The electron binding energy of the active component of the catalyst is shown in [reference needed]. Figure 1 .

[0074] 2. Catalyst Evaluation

[0075] In a fixed bed, the catalyst NiB prepared above was reduced by hydrogen gas at atmospheric pressure and 450°C for 6 hours. Using C4 olefins from the MTO process with aldehydes and ketones containing 200 ppm of oxygen as feedstock, the reaction temperature was 60°C, the reaction pressure was 2.0 MPa, and the volume hourly space velocity was 1.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0076] Example 3

[0077] 1. Catalyst Preparation

[0078] Nickel nitrate was prepared into a nickel-ammonium solution (13.8 wt% nickel). 30 g of alumina support was mixed with 42 g of the nickel-ammonium solution for 3 h, and dried at 60 °C and 100 °C for 4 h respectively. Then, the solution was immersed in 30 g of potassium borohydride aqueous solution (50 wt%) and stirred slowly until no more bubbles were generated. The solution was washed several times with deionized water and dried at 80 °C for 4 h to obtain the NiB catalyst, where the molar ratio of B to Ni was approximately 1.52. The electron binding energy of the active component of the catalyst is shown in [reference needed]. Figure 1 .

[0079] 2. Catalyst Evaluation

[0080] In a fixed bed, the catalyst NiB prepared above was reduced by hydrogen gas at atmospheric pressure and 450°C for 6 hours. Using C4 olefins from the MTO process with aldehydes and ketones containing 200 ppm of oxygen-containing compounds as feedstock, the reaction temperature was 60°C, the reaction pressure was 1.6 MPa, and the volume hourly space velocity was 1.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0081] Example 4

[0082] 1. Catalyst Preparation

[0083] Nickel nitrate was prepared into a nickel-ammonium solution (13.8 wt% nickel). 30 g of alumina support was mixed with 42 g of the nickel-ammonium solution for 3 h, and dried at 60 °C and 100 °C for 4 h respectively. Then, the solution was immersed in 60 g of potassium borohydride aqueous solution (50 wt%) and stirred slowly until no more bubbles were generated. The solution was washed several times with deionized water and dried at 80 °C for 4 h to obtain the NiB catalyst, where the molar ratio of B to Ni was approximately 3.04. The electron binding energy of the active component of the catalyst is shown in [reference needed]. Figure 1 .

[0084] 2. Catalyst Evaluation

[0085] In a fixed bed, the catalyst NiB prepared above was reduced by hydrogen gas at atmospheric pressure and 450°C for 6 hours. Using C4 olefins from the MTO process with aldehydes and ketones containing 200 ppm of oxygen-containing compounds as feedstock, the reaction temperature was 60°C, the reaction pressure was 1.6 MPa, and the volume hourly space velocity was 1.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0086] Comparative Example 1

[0087] 1. Catalyst Preparation

[0088] The catalyst preparation differs from that in Example 1 in that potassium borohydride was not added.

[0089] Everything else is the same as in Example 1.

[0090] 2. Catalyst Evaluation

[0091] In a fixed-bed reactor, a Pd catalyst was used, and hydrogen was introduced for reduction at atmospheric pressure and 450℃ for 6 hours. C4 olefins from the MTO process, with an aldehyde / ketone oxygen-containing compound concentration of 200 ppm, were used as feedstock. The reaction temperature was 45℃, the reaction pressure was 0.6 MPa, and the volume hourly space velocity (VHSV) was 2.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0092] Comparative Example 2

[0093] 1. Catalyst Preparation

[0094] The catalyst preparation differs from that in Example 2 in that potassium borohydride was not added.

[0095] Everything else is the same as in Example 1.

[0096] 2. Catalyst Evaluation

[0097] In a fixed-bed reactor, a Ni catalyst was used, and hydrogen was introduced at atmospheric pressure and 450°C for 6 hours for reduction. C4 olefins from the MTO process, with an aldehyde / ketone oxygen-containing compound concentration of 200 ppm, were used as feedstock. The reaction temperature was 60°C, the reaction pressure was 2.0 MPa, and the volume hourly space velocity (VHSV) was 1.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0098] Comparative Example 3

[0099] 1. Catalyst Preparation

[0100] The difference between the catalyst preparation method in Example 2 and Example 3 is that the alumina support was treated with an aqueous solution of potassium borohydride instead of the active component; the specific method is as follows:

[0101] 30g of alumina support was immersed in 20g of potassium borohydride aqueous solution (25wt%) for 1h, stirred slowly, and dried at 80℃ for 4h. Then, the potassium borohydride-treated alumina support was mixed with 42g of nickel ammonium solution (13.8wt% nickel), and dried at 60℃ and 100℃ for 4h respectively to obtain the Ni catalyst.

[0102] 2. Catalyst Evaluation

[0103] In a fixed-bed reactor, a Ni catalyst was used, and hydrogen was introduced at atmospheric pressure and 450°C for 6 hours for reduction. C4 olefins from the MTO process, with an aldehyde / ketone oxygen-containing compound concentration of 200 ppm, were used as feedstock. The reaction temperature was 60°C, the reaction pressure was 2.0 MPa, and the volume hourly space velocity (VHSV) was 1.0 h⁻¹. -1 The results of hydroisomerization are shown in Table 1.

[0104] Table 1

[0105]

[0106] Figure 1The X-ray photoelectron spectroscopy (XPS) spectra of Examples 2-4 and Comparative Example 2 show that boron acts on the active component nickel, causing a shift in the electron binding energy of nickel on the catalyst surface. The degree of this shift varies depending on the boron content. This change in the electronic state of the active component nickel promotes the isomerization of 1-butene and the hydrogenation activity of 1,3-dibutene, thus facilitating the reaction.

[0107] Compared with Example 1, the conversion rate of 1-butene in Comparative Example 1 was 24.0% and the conversion rate of 1,3-butadiene was 87.2%, demonstrating that no borohydride acted on the active component palladium, the reactivity of hydroisomerization was very low, and the selective hydrogenation activity of 1,3-butadiene was very low.

[0108] Compared to Example 2, Comparative Example 2 showed a 1-butene conversion rate of 14.5% and a 1,3-butadiene conversion rate of 74.2%, which also demonstrated that no borohydride acted on the active component nickel, resulting in lower hydroisomerization reactivity and lower selective hydrogenation reactivity of 1,3-butadiene.

[0109] Compared with Example 1, Comparative Example 3 modified the support with borohydride without acting on the active component. Its 1-butene conversion rate was 14.6% and its 1,3-butadiene conversion rate was 73.0%, indicating that only when boron acts on the active component can the reactivity of hydroisomerization and the selective hydrogenation activity of 1,3-butadiene be improved.

[0110] The conversion rates of 1-butene in Examples 1-4 were 62.2-67.5%, the selectivity of 2-butene was 97.5-98.8%, and the conversion rate of 1,3-butadiene reached 98.9-99.5%. This demonstrates that the hydroisomer catalyst prepared in this invention can overcome the inhibition of catalyst activity by oxygen-containing compounds, achieve efficient utilization of C4 by-products of MTO, improve its capacity utilization rate, and has high industrial application and economic value.

Claims

1. The application of a supported catalyst in the hydroisomerization reaction of C4 olefins to prepare 1-butene or 2-butene, wherein the supported catalyst comprises a support, an active component, and an auxiliary agent; the support is at least one selected from silicon oxide, alumina, manganese oxide, zinc oxide, calcium oxide, and activated carbon; the active component comprises a metal element; the metal element is at least one selected from iron, copper, nickel, cobalt, and palladium; the active component, based on the mass of the metal element, accounts for 0.01~20 wt% of the total mass of the catalyst; the auxiliary agent is boron, and based on boron element, the molar ratio to the metal element is 0.3~10, wherein the boron element is loaded onto the catalyst after the active component is loaded onto the support to form a catalyst precursor, and acts on the active component metal element after the support is loaded; the boron precursor is at least one selected from borohydride, borane, boric acid, and their salts; the support accounts for 50.0%~99.9% of the total mass of the supported catalyst.

2. The application as described in claim 1, characterized in that: The active component, based on the mass of the metal element therein, accounts for 0.5% to 16% of the total mass of the catalyst; and / or, The additive, calculated as boron, has a molar ratio of 0.5 to 4 with the metal element; and / or, The support comprises 75.0% to 99.5% of the total mass of the catalyst; and / or, The precursor of the metal element in the active component is a salt of the metal element.

3. The application as described in claim 1, characterized in that: The precursor of the metal element in the active component is at least one of nitrate, chloride, acetate, sulfate, and carbonate.

4. The application as described in claim 1, characterized in that: The borohydride is an alkali metal borohydride.

5. The application as described in claim 4, characterized in that: The borohydride is at least one of potassium borohydride and sodium borohydride.

6. The application as described in claim 1, characterized in that: The preparation method of the supported catalyst includes the following steps: (1) The support and the aqueous solution of the precursor of the metal element are mixed evenly, and the catalyst precursor is obtained after dehydration and drying. (2) The catalyst precursor obtained in step (1) is added to the precursor aqueous solution of the auxiliary agent, mixed evenly, and then washed and dried to obtain the supported catalyst.

7. The application as described in claim 6, characterized in that: Step (1), The concentration of the aqueous solution of the metal element precursor is 0.1~15wt%; and / or, The concentration of the precursor aqueous solution of the adjuvant is 0.1~60wt%; and / or, The precursor aqueous solution of the auxiliary agent is a boron precursor aqueous solution, wherein the molar ratio of boron to the metal element is 0.3~20; and / or, The mixing time between the carrier and the aqueous precursor solution of the metal element is 0.1–12 h; and / or, The drying temperature is 60~120℃; and / or, The drying time is 6 to 10 hours.

8. The application as described in claim 7, characterized in that: Step (1), The concentration of the aqueous solution of the metal element precursor is 0.2~14wt%; and / or, The concentration of the precursor aqueous solution of the adjuvant is 1~50wt%; and / or, The molar ratio of boron to the metal element in the aqueous precursor solution is 1-8; and / or, The mixing time between the carrier and the aqueous precursor solution of the metal element is 1-3 h; and / or, The drying time is 6-8 hours.

9. The application as described in claim 6, characterized in that: Step (2), Stir until the solution no longer produces bubbles during mixing; and / or, Wash with deionized water; and / or, The drying temperature is 60~120℃; and / or, The drying time is 4 to 8 hours.

10. The application as described in claim 9, characterized in that: Step (2), The drying temperature is 60~80℃.

11. The application as described in claim 1, characterized in that: The method for preparing 1-butene or 2-butene by hydroisomerization of C4 olefins includes the following steps: a) Hydroisomerization unit, using the supported catalyst, selectively hydrogenates 1,3-butadiene in a C4 olefin to 1-butene while isomerizing 1-butene to 2-butene via hydroisomerization. Optionally, b) the isomerization unit, isomerizing 2-butene to 1-butene; Optionally, c) select a hydrogenation unit to selectively hydrogenate 1,3-butadiene to 1-butene.

12. The application as described in claim 11, characterized in that: The carbotetraene is a carbotetraene containing an oxygen-containing compound; the oxygen-containing compound is at least one of aldehydes, ketones, or other oxygen-containing compounds; and / or, The oxygen-containing compound content in the C4 olefin is above 200 ppm.

13. The application as described in claim 12, characterized in that: The C4 olefin is a C4 byproduct obtained from the methanol-to-olefins process.

14. The application as described in claim 11, characterized in that: Step a). The reaction temperature is 30~100℃; and / or, The reaction pressure is 0.1~5 MPa; Volumetric hourly space velocity (VHSV) is 0.1–10 h⁻¹ -1 .

15. The application as described in claim 14, characterized in that: Step a). The reaction temperature is 40~70℃; and / or, The reaction pressure is 0.4~2.5 MPa; Volumetric hourly space velocity is 0.8–2 h⁻¹ -1 .

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