A method for saturated hydrogenation of C4 fraction

Abstract

The present invention provides a method for saturated hydrogenation of a C4 fraction, comprising: contacting the C4 fraction with a hydrogenation catalyst, thereby causing a hydrogenation reaction of unsaturated hydrocarbons in the C4 fraction to generate alkanes, wherein the hydrogenation reaction is completed in a reactor, and the hydrogenation catalyst comprises a composite oxide carrier and an active component loaded on the composite oxide carrier, and the active component comprises molybdenum and / or molybdenum oxide and nickel and / or nickel oxide. The present invention can reduce the content of unsaturated hydrocarbons in the raw material and improve the added value of the product by using a molybdenum-nickel-based catalyst with good low-temperature activity to hydrogenate the C4 fraction at a relatively low inlet temperature. In addition, the molybdenum-nickel-based catalyst used in the present invention has strong resistance to impurities and can improve operational stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalytic hydrogenation of low-carbon hydrocarbons and mainly relates to a C 4 Method for saturation hydrogenation of distillates. Background Art

[0002] The petroleum hydrocarbon cracking ethylene production unit produces a large amount of mixed C4 fractions as by-products, which contain 40wt% to 60wt% of 1,3-butadiene, 0.5 to 2.0wt% of vinyl acetylene (VA) and ethyl acetylene (EA), and the rest are butane, butene and a small amount of 1,2-butadiene, C3 and C5 components. In industry, 1,3-butadiene is generally separated from C4 by extraction and other methods. In the ethylene production unit with a synthetic rubber unit downstream, the by-product cracked C4 is passed through a 1,3-butadiene extraction unit to obtain a butadiene product. The tail gas produced contains 20 to 30wt% of 1,3-butadiene, 4 to 8wt% of 1,2-butadiene, and 20 to 40wt% of vinyl acetylene (VA) and ethyl acetylene (EA). This type of tail gas is characterized by a high content of acetylene and is difficult to handle. In industry, it is generally mixed with liquefied gas and burned as flare gas, which not only wastes resources but also pollutes the environment.

[0003] This butadiene and alkyne content C 4 There are generally two ways to utilize the fraction: one is to perform selective hydrogenation to increase the content of butadiene or butene-1 and other monoolefins; the existing technology uses C 4 The catalyst for the selective hydrogenation of carbon tetraacetylene in the fraction is mainly a precious metal catalyst with palladium as the main active component. The precious metal catalyst has high activity and high selectivity for butadiene. However, with the continuous rise in the price of precious metals, the catalyst cost is very high. At the same time, the resistance of precious metal catalysts to impurities and the operating stability are not as good as those of non-precious metal hydrogenation catalysts represented by nickel. One method is to use a two-stage hydrogenation process to hydrogenate all unsaturated hydrocarbons such as alkynes, dienes and monoolefins into alkanes to become high-quality ethylene cracking materials.

[0004] CN103787811 proposes a method for hydrogenating butadiene tail gas, using a two-stage reactor to treat a C4 fraction containing unsaturated hydrocarbons, first absorbing the tail gas, then using a Ni-based catalyst for liquid phase hydrogenation, and then using a Ni-Mo-based catalyst for gas phase hydrogenation reaction. This method has a good hydrogenation effect and a low olefin content in the product, but the second stage uses a molybdenum-based hydrogenation refining catalyst, the reaction temperature is high, it is a gas phase reaction, the energy consumption is too large, and a solvent is used to adsorb C4, and subsequent separation requires additional equipment investment for distillation, which further increases energy consumption.

[0005] Another problem is that the existing technologies are all focused on hydrogenating the C4 fraction with high content of dienes and alkynes. However, petrochemical enterprises often have a C4 fraction raw material with low diene content, such as etherified C4 or isononanol C4, which has low recovery and processing value. Directly feeding it into the ethylene cracking furnace as a raw material will affect the stability of the cracking furnace due to the high olefin content. Therefore, it is urgently needed to carry out hydrogenation saturation. However, the treatment of such raw materials in the market is generally carried out by gas phase hydrogenation treatment using molybdenum-nickel hydrogenation catalysts at high inlet temperatures. Due to the huge energy consumption and inconvenience in operation caused by the vaporization of the raw materials, it leads to large investment, high energy consumption and low efficiency. Summary of the invention

[0006] In order to solve the technical problems of large investment and high energy consumption in the current technology, the purpose of the present invention is to provide a C 4 The present invention uses a molybdenum-nickel-based catalyst with good low-temperature activity to saturate the C 4 The fraction is subjected to hydrogenation treatment, which can reduce the content of unsaturated hydrocarbons in the raw material and increase the added value of the product. In addition, the molybdenum-nickel-based catalyst used in the present invention has strong impurity resistance and can improve operation stability.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] A C 4 The method for saturated hydrogenation of a fraction comprises: 4 The fraction is contacted with a hydrogenation catalyst, thereby 4 The unsaturated hydrocarbons in the fraction undergo a hydrogenation reaction to generate alkanes, wherein the hydrogenation reaction is completed in a reactor, and the hydrogenation catalyst includes a composite oxide carrier and an active component supported on the composite oxide carrier, and the active component includes molybdenum and / or molybdenum oxide and nickel and / or nickel oxide.

[0009] According to some preferred embodiments of the present invention, the active component further includes cobalt and / or cobalt oxide.

[0010] According to some preferred embodiments of the present invention, the hydrogenation reaction is carried out under liquid phase conditions.

[0011] According to some preferred embodiments of the present invention, the pressure of the reactor is controlled to be 2.0 MPa to 3.5 MPa; and the inlet temperature is controlled to be 60° C. to 90° C., so as to achieve the liquid phase condition.

[0012] According to some preferred embodiments of the present invention, the operating conditions of the reactor also include: a volumetric space velocity of 0.3h -1 ~2.0h -1; The volume ratio of hydrogen to fresh raw material is 30 to 300:1; the circulation ratio is 5 to 15:1.

[0013] In the present invention, the term "fresh raw material" refers to newly added C 4 Fraction.

[0014] In the present invention, the term "circulation ratio" refers to the volume ratio of the recycled material to the fresh raw material.

[0015] In the present invention, the outlet temperature varies with the inlet temperature and the circulation ratio.

[0016] According to some preferred embodiments of the present invention, the C 4 In the fraction, the content of monoolefins is 5wt% to 50wt%, and the content of diolefins is not higher than 1wt%.

[0017] According to some preferred embodiments of the present invention, the C 4 The fraction comes from the ether C 4 Or the isononyl alcohol device extracts the residual C 4 .

[0018] According to some preferred embodiments of the present invention, the composite oxide support is selected from Al 2 O 3 -TiO 2 Composite oxide support, TiO 2 -ZrO 2 Composite oxide support, TiO 2 -SiO 2 Composite oxide supports and Al 2 O 3 -TiO 2 -ZrO 2 At least one of the composite oxide supports.

[0019] According to some preferred embodiments of the present invention, the composite oxide support is Al 2 O 3 -TiO 2 The composite oxide support is based on the Al 2 O 3 -TiO 2 The weight of the composite oxide support is used as the calculation basis, Al 2 O 3 The content of TiO is 70wt% to 90wt%, 2 The content of Al is 10wt% to 30wt%; preferably, Al 2 O 3 The content of TiO is 70wt% to 80wt%, 2 The content is 20wt% to 30wt%.

[0020] According to the present invention, the Al 2 O 3 -TiO 2 The composite oxide is preferably a titanium oxide-aluminum oxide composite carrier provided in patent CN104971706B.

[0021] According to some preferred embodiments of the present invention, the composite oxide support is Al 2 O 3 -TiO 2 -ZrO 2 The composite oxide support is based on the Al 2 O 3 -TiO 2 -ZrO 2 The weight of the composite oxide support is used as the calculation basis, Al 2 O 3 The content of TiO is 65wt% to 75wt%, 2 The content of ZrO is 15wt% to 25wt%, 2 The content is 5wt% to 15wt%.

[0022] In some preferred embodiments of the present invention, the Al 2 O 3 -TiO 2 -ZrO 2 In the composite support, TiO 2 With ZrO 2 The mass ratio of TiO is (3-5):1, preferably (3.5-4.5):1. 2 With ZrO 2 When the mass ratio of is within the above range, it is beneficial to reduce the inlet temperature of the reactor and improve the hydrogenation efficiency.

[0023] According to some preferred embodiments of the present invention, based on the total mass of the hydrogenation catalyst, the content of molybdenum and / or molybdenum oxide is 8wt% to 20wt%; the content of nickel and / or nickel oxide is 4wt% to 12wt%; and the content of cobalt and / or cobalt oxide is 1wt% to 5wt%.

[0024] According to some preferred embodiments of the present invention, the method for preparing the hydrogenation catalyst comprises:

[0025] S1. impregnating the composite oxide with an impregnation solution containing molybdenum, and drying and calcining the impregnated product to obtain a catalyst precursor;

[0026] S2. The catalyst precursor is impregnated with an impregnation solution containing nickel, preferably nickel and cobalt, and the impregnation product is dried and calcined to obtain the hydrogenation catalyst.

[0027] According to some preferred embodiments of the present invention, in step S1, the calcination treatment conditions include a temperature of 450°C to 650°C, preferably 500°C to 600°C; and a time of 1h to 24h, preferably 2h to 12h.

[0028] According to some preferred embodiments of the present invention, in step S2, the calcination treatment conditions include a temperature of 450°C to 650°C, preferably 500°C to 600°C; and a time of 1h to 24h, preferably 2h to 12h.

[0029] According to some preferred embodiments of the present invention, before the hydrogenation reaction, the hydrogenation catalyst is subjected to a sulfurization treatment, and the conditions of the sulfurization treatment include: a hydrogen pressure of 2.0 MPa to 3.5 MPa, a hydrogen-oil ratio of 300 to 500:1, a sulfurization temperature of 240°C to 350°C, and a volume space velocity of the sulfurized oil of 2h -1 ~5h -1 The sulfide oil introduction time is 10h to 30h.

[0030] According to the present invention, the hydrogenation catalyst of the present invention can be sulfided at a relatively low sulfiding temperature, for example, at a temperature as low as 240°C.

[0031] According to some preferred embodiments of the present invention, the sulfided oil contains dimethyl disulfide. More preferably, based on the total mass of the hydrogenation catalyst, the content of dimethyl disulfide is 0.1 wt% to 5 wt%.

[0032] The beneficial effects of the present invention are at least in the following aspects:

[0033] First, the present invention avoids C 4 The process problems caused by the vaporization of the fraction under high temperature conditions are reduced, the energy consumption is reduced, the device operating conditions are easy to achieve, and it has good operability. In addition, the inventors found that compared with the minimum reactor inlet temperature of 160-170°C reported in the literature for the hydrogenation of C4 monoolefins using nickel-molybdenum-based hydrogenation catalysts, the molybdenum-nickel-based hydrogenation refining catalyst using an alumina-titania composite carrier can reduce the reactor startup temperature to 80°C, thus avoiding the C 4 The process problems caused by the vaporization of the fraction under high temperature conditions reduce energy consumption, and the catalyst has a high resistance to impurities (such as sulfides, nitrides, and chlorine), which can ensure the long-term stable operation of the catalyst.

[0034] Secondly, the hydrogenation method of the present invention can be used to treat C 4 Logistics, such as C4 after etherification, C4 after extraction of isononanol, C 4 The mono-olefin content of the stream may be below 3 wt%, preferably below 0.5 wt%. DETAILED DESCRIPTION

[0035] The present invention is described in detail below by way of examples, but the protection scope of the present invention is not limited to the following description.

[0036] In the following embodiments and the present invention, the term " / " represents a relationship of and.

[0037] In the following embodiments, unless otherwise specified, the components of the hydrogenated material are analyzed when the device is running for 96 hours.

[0038] In the following embodiments, unless otherwise specified, the content of each substance in the hydrogenation product is detected by gas chromatography.

[0039] In the following embodiments, unless otherwise specified, the content of active components in the catalyst is detected by X-ray fluorescence (XRF) analysis.

[0040] Example 1

[0041] A. Preparation of hydrogenation catalyst

[0042] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0043] 178.5 g of AlCl 3 6H 2 O (analytical grade) was placed in 1000 mL of deionized water to prepare solution A1; 430.7 g of Ti(OCH 2 CH 3 ) 4 (chemically pure) was dissolved in 500 mL of benzene (benzene content: 99.8 wt%) to prepare solution B1; 18 g of NH 4 HCO 3 (analytical grade) was dissolved in 600 mL of deionized water, and then 250 mL of 26 wt% ammonia water was added, stirred evenly, and then a certain volume of deionized water was added to prepare 1000 mL of solution C1.

[0044] Under normal pressure and temperature of 73°C, three solutions A1, B1 and C1 were co-precipitated in parallel. The flow rate of solution C1 was controlled to keep the pH value of the precipitate in the range of 5.0-6.0 for 8 minutes, and the flow rate of solution C1 was increased to keep the pH value of the mixed solution in the range of 8.5-9.5 for 8 minutes, and then the flow rate of solution C1 was reduced to keep the pH value of the mixed solution in the range of 5.0-6.0 for 8 minutes, and the flow rate of solution C1 was increased to keep the pH value of the precipitate in the range of 8.5-9.5, and this process was repeated until all solutions A1 and B1 were added dropwise to obtain a reaction solution.

[0045] The obtained reaction solution was allowed to stand at 70°C for 30 minutes and then filtered to obtain a filter cake. The filter cake was then washed with deionized water 15 times the volume of the filter cake for 30 minutes, filtered again, and washed again. This process was repeated four times. Finally, the filter cake was dried at 110°C for 10 hours and then calcined at 450°C for 5 hours to obtain 42.7 g of Al 2 O 3 -TiO 2 Composite oxide support (named Z1). Among them, TiO 2 The content of is 15.14%, and the balance is Al 2 O 3 .

[0046] b) Loading of active ingredients

[0047] Use a volumetric flask and 14 wt% ammonia water to prepare 26.68 g / 100 ml of ammonium molybdate tetrahydrate, and impregnate 100 g of the carrier Z1 obtained in step a) at room temperature for 2 hours. After filtering, dry it at 110°C overnight and calcine it at 550°C for 4 hours to complete the loading of the active component molybdenum oxide.

[0048] Then, Z1 loaded with molybdenum oxide was placed in 39.48 g / 100 ml nickel nitrate hexahydrate and 11.62 g / 100 ml cobalt nitrate hexahydrate solution, immersed at room temperature for 2 h, filtered, dried at 110 ° C overnight, and calcined at 550 ° C for 4 h to obtain MoO 3 MoO with a content of 14.1wt%, CoO content of 1.9wt%, and NiO content of 7.5wt% 3 -CoO-NiO / Al 2 O 3 -TiO 2 Catalyst C1.

[0049] B. Hydrogenation reaction

[0050] The C4 raw material A was extracted from a certain isononanol unit, and the raw material composition is as follows:

[0051] Butene-1: 0.44wt%; trans-butene: 10.31wt%; isobutylene: 4.03wt%; isobutane: 11.43wt%; n-butane: 72.46wt%; cis-butene: 0.32wt%; butadiene: <1wt%.

[0052] After sorting, the following results were obtained: diolefins: <1wt%; monoolefins: 15.1wt%; and the remainder being alkanes.

[0053] A 100 mL fixed bed reactor was loaded with 100 mL of hydrogenation catalyst C1 for sulfidation reaction. The sulfidation conditions were as follows: hydrogen pressure 2.0 MPa, hydrogen-to-oil ratio 300-500:1, and temperature 250°C for 2 h. -1 Sulfurized oil containing 3 wt% of dimethyl disulfide (DMDS) was passed into the reactor for 15 h at a log volume space velocity of .

[0054] The hydrogenation reaction was carried out after the sulfidation reaction. The operating conditions of the hydrogenation reactor were: pressure 2.8 MPa, inlet temperature 80 °C, volumetric space velocity 2.0 h -1 The volume ratio of hydrogen to fresh raw material is 160:1, and the circulation ratio is 1:1.

[0055] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 0.1wt%.

[0056] Example 2

[0057] A. Preparation of hydrogenation catalyst

[0058] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0059] Same as Example 1.

[0060] b) Loading of active ingredients

[0061] According to the loading method in Example 1, the amount of ammonium molybdate tetrahydrate and nickel nitrate hexahydrate was adjusted to obtain MoO 3 MoO with a content of 14.1wt% and NiO with a content of 7.5wt% 3 -NiO / Al 2 O 3 -TiO 2 Catalyst C2.

[0062] B. Hydrogenation reaction

[0063] Using etherified C4 raw materials, the raw material composition is as follows:

[0064] Butene-1: 0.22wt%; trans-butene: 35.62wt%; isobutylene: <0.01wt%; isobutane: 16.35wt%; n-butane: 35.87wt%; cis-butene: 11.08wt%; butadiene <0.1wt%.

[0065] After sorting, the content of dienes is less than 0.1 wt %; monoolefins are 46.92 wt %; and the remainder is alkanes.

[0066] A 100 mL scale fixed bed reactor was loaded with 100 mL of hydrogenation catalyst C1 for sulfidation reaction. The sulfidation conditions were as follows: hydrogen pressure 2.0 MPa, hydrogen-to-oil ratio 300-500:1, and temperature 300°C for 2 h. -1 Sulfurized oil containing 2 wt % of dimethyl disulfide (DMDS) was passed through for 18 h at a log volume space velocity of .

[0067] The hydrogenation reaction was carried out after the sulfidation reaction. The operating conditions of the hydrogenation reactor were: pressure 3.5 MPa, inlet temperature 90 °C, volume space velocity 0.5 h -1 The volume ratio of hydrogen to fresh raw material is 160:1, and the circulation ratio is 12:1.

[0068] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 0.1wt%.

[0069] Example 3

[0070] A. Preparation of hydrogenation catalyst

[0071] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0072] Same as Example 1.

[0073] b) Loading of active ingredients

[0074] According to the loading method in Example 1, the amounts of ammonium molybdate tetrahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate were adjusted to obtain MoO 3 MoO with a content of 11wt%, CoO content of 2wt%, and NiO content of 8wt% 3 -CoO-NiO / Al 2 O 3 -TiO 2 Catalyst C3.

[0075] B. Hydrogenation reaction

[0076] The etherified C4 raw material in Example 2 was used.

[0077] The sulfidation treatment was carried out in the same manner as in Example 2, followed by hydrogenation treatment, with the operating conditions being a pressure of 2.2 MPa, an inlet temperature of 70°C, and a volumetric space velocity of 0.5 h -1 The volume ratio of hydrogen to fresh raw material is 180:1, and the circulation ratio is 5:1.

[0078] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 0.3wt%.

[0079] Example 4

[0080] A. Preparation of hydrogenation catalyst

[0081] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0082] Same as Example 1.

[0083] b) Loading of active ingredients

[0084] According to the loading method in Example 1, the amounts of ammonium molybdate tetrahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate were adjusted to obtain MoO 3 MoO with a content of 12wt%, CoO content of 4wt%, and NiO content of 6wt% 3 -CoO-NiO / Al 2 O 3 -TiO 2 Catalyst C4.

[0085] B. Hydrogenation reaction

[0086] The etherified C4 raw material in Example 2 was used.

[0087] The sulfidation treatment was carried out in the same manner as in Example 2, followed by hydrogenation treatment, with the operating conditions being a pressure of 2.5 MPa, an inlet temperature of 60°C, and a volumetric space velocity of 0.5 h -1 The volume ratio of hydrogen to fresh raw material is 180:1, and the circulation ratio is 6:1.

[0088] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 0.5wt%.

[0089] Example 5

[0090] A. Preparation of hydrogenation catalyst

[0091] a) TiO 2 -ZrO 2 Preparation of composite oxide supports

[0092] The TiO2 -ZrO 2 Composite carrier.

[0093] b) Loading of active ingredients

[0094] According to the loading method in Example 1, the amounts of ammonium molybdate tetrahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate were adjusted to obtain MoO 3 MoO with a content of 10.5wt%, CoO content of 1.5wt%, and NiO content of 11wt% 3 -CoO-NiO / Al 2 O 3 -TiO 2 Catalyst C5.

[0095] B. Hydrogenation reaction

[0096] The etherified C4 raw material in Example 2 was used.

[0097] The sulfidation treatment was carried out in the same manner as in Example 2, followed by hydrogenation treatment, with the operating conditions being a pressure of 2.5 MPa, an inlet temperature of 60°C, and a volumetric space velocity of 0.5 h -1 The volume ratio of hydrogen to fresh raw material is 200:1, and the circulation ratio is 9:1.

[0098] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 1.3wt%.

[0099] Example 6

[0100] A. Preparation of hydrogenation catalyst

[0101] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0102] Same as Example 1.

[0103] b) Loading of active ingredients

[0104] 100 g of the carrier Z1 prepared in step a) was placed in 39.48 g / 100 ml of nickel nitrate hexahydrate, 11.62 g / 100 ml of cobalt nitrate hexahydrate and 26.68 g / 100 ml of ammonium molybdate tetrahydrate solution, immersed at room temperature for 2 h, filtered and dried at 110 ° C overnight, and calcined at 550 ° C for 4 h to complete the loading of active components to obtain MoO 3 MoO with a content of 14.1wt%, CoO content of 1.9wt%, and NiO content of 7.5wt% 3 -CoO-NiO / Al 2 O 3-TiO 2 Catalyst C6.

[0105] B. Hydrogenation reaction

[0106] The hydrogenation reaction was carried out under exactly the same conditions as in Example 1. The product composition at the reactor outlet was free of alkynes and dienes, and the monoolefin content was 0.82 wt%.

[0107] Example 7

[0108] In this embodiment, MoO 3 MoO with a content of 14.1wt%, CoO content of 1.9wt%, and NiO content of 7.5wt% 3 -CoO-NiO / Al 2 O 3 -TiO 2 -ZrO 2 Catalyst C7. Among them, Al 2 O 3 -TiO 2 -ZrO 2 In, Al 2 O 3 The content is 70wt%, TiO 2 The content is 24wt%, ZrO 2 The content is 6wt%.

[0109] Except that the inlet temperature was 70° C., the other hydrogenation conditions were the same as those in Example 1. The composition of the product at the reactor outlet was measured: no alkynes and dienes, and the monoolefin content was 0.06 wt%.

[0110] Comparative Example 1

[0111] A. Preparation of hydrogenation catalyst

[0112] a) γ-Al 2 O 3 Preparation of vector

[0113] The γ-Al 2 O 3 carrier.

[0114] b) Loading of active ingredients

[0115] According to the loading method in Example 1, the amounts of ammonium molybdate tetrahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate were adjusted to obtain MoO 3 MoO with a content of 10.5wt%, CoO content of 1.5wt%, and NiO content of 11wt% 3 -CoO-NiO / Al 2 O 3 -TiO2 Catalyst DC1.

[0116] B. Hydrogenation reaction

[0117] The etherified C4 raw material in Example 2 was used.

[0118] The sulfidation treatment was carried out in the same manner as in Example 2, followed by hydrogenation treatment, with the operating conditions being a pressure of 2.5 MPa, an inlet temperature of 60°C, and a volumetric space velocity of 0.5 h -1 The volume ratio of hydrogen to fresh raw material is 200:1, and the circulation ratio is 9:1.

[0119] Reactor outlet product composition: no alkynes and dienes, monoolefin content is 17wt%.

[0120] Comparative Example 2

[0121] A. Preparation of hydrogenation catalyst

[0122] a)Al 2 O 3 -TiO 2 Preparation of composite oxide supports

[0123] Same as Example 1.

[0124] b) Loading of active ingredients

[0125] According to the loading method in Example 1, the amount of nickel nitrate hexahydrate was adjusted to obtain NiO / Al with a NiO content of 22 wt%. 2 O 3 -TiO 2 Catalyst DC2.

[0126] B. Hydrogenation reaction

[0127] The hydrogenation reaction was carried out under exactly the same conditions as in Example 2. The product composition at the reactor outlet was free of alkynes and dienes, and the monoolefin content was 10.3 wt%.

[0128] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for saturated hydrogenation of a C4 fraction, comprising: The C4 fraction is contacted with a hydrogenation catalyst, so that the unsaturated hydrocarbons in the C4 fraction undergo a hydrogenation reaction to generate alkanes, wherein the hydrogenation reaction is completed in a reactor, the hydrogenation catalyst comprises a composite oxide carrier and an active component supported on the composite oxide carrier, the active component comprises molybdenum and / or molybdenum oxide and nickel and / or nickel oxide; the hydrogenation reaction is carried out under liquid phase conditions; the composite oxide carrier is selected from at least one of an Al2O3-TiO2 composite oxide carrier, a TiO2-ZrO2 composite oxide carrier and an Al2O3-TiO2-ZrO2 composite oxide carrier; In the C4 fraction, the content of monoolefins is 5wt% to 50wt%, and the content of diolefins is not higher than 1wt%; Based on the total mass of the hydrogenation catalyst, the content of molybdenum and / or molybdenum oxide is 8wt%~20wt%; the content of nickel and / or nickel oxide is 4wt%~12wt%.

2. The method according to claim 1, characterized in that The pressure of the reactor is controlled to be 2.0 MPa-3.5 MPa; the inlet temperature is controlled to be 60° C.-90° C., so as to achieve the liquid phase condition.

3. The method according to claim 2, characterized in that The operating conditions of the reactor also include: a volume space velocity of 0.3h -1 ~2.0h -1 ; The volume ratio of hydrogen to fresh raw material is 30~300:1; the circulation ratio is 5~15:

1.

4. The method according to claim 1, characterized in that: The C4 fraction is derived from the C4 after etherification or the residual C4 of the isononanol unit.

5. The method according to claim 1, characterized in that The composite oxide carrier is an Al2O3-TiO2 composite oxide carrier. Based on the weight of the Al2O3-TiO2 composite oxide carrier as a calculation basis, the content of Al2O3 is 70wt%~90wt%, and the content of TiO2 is 10wt%~30wt%.

6. The method according to claim 1, characterized in that The composite oxide carrier is an Al2O3-TiO2 composite oxide carrier. Based on the weight of the Al2O3-TiO2 composite oxide carrier as a calculation basis, the content of Al2O3 is 70wt%~80wt%, and the content of TiO2 is 20wt%~30wt%.

7. The method according to claim 1, characterized in that The composite oxide carrier is an Al2O3-TiO2-ZrO2 composite oxide carrier. Based on the weight of the Al2O3-TiO2-ZrO2 composite oxide carrier, the content of Al2O3 is 65wt%~75wt%, the content of TiO2 is 15wt%~25wt%, and the content of ZrO2 is 5wt%~15wt%.

8. The method according to any one of claims 1 to 7, characterized in that: The active component also includes cobalt and / or cobalt oxide.

9. The method according to claim 8, characterized in that Based on the total mass of the hydrogenation catalyst, the content of molybdenum and / or molybdenum oxide is 8wt%~20wt%; the content of nickel and / or nickel oxide is 4wt%~12wt%; and the content of cobalt and / or cobalt oxide is 1wt%~5wt%.

10. The method according to any one of claims 1 to 7 and 9, characterized in that: The preparation method of the hydrogenation catalyst comprises: S1. impregnating the composite oxide with an impregnation solution containing molybdenum, and drying and calcining the impregnated product to obtain a catalyst precursor; S2. The catalyst precursor is impregnated with an impregnation solution containing nickel, and the impregnation product is dried and calcined to obtain the hydrogenation catalyst.

11. The method according to claim 10, characterized in that In step S2, the catalyst precursor is impregnated with an impregnation solution containing nickel and cobalt elements.

12. The method according to claim 10, characterized in that In step S1, the conditions for the calcination treatment include a temperature of 450°C to 650°C and a time of 1 hour to 24 hours; and / or in step S2, the conditions for the calcination treatment include a temperature of 450°C to 650°C and a time of 1 hour to 24 hours.

13. The method according to claim 12, characterized in that In step S1, the conditions for the calcination treatment include a temperature of 500°C to 600°C and a time of 2h to 12h; and / or in step S2, the conditions for the calcination treatment include a temperature of 500°C to 600°C and a time of 2h to 12h.

14. The method according to any one of claims 1-7, 9, 11-13, characterized in that: Before the hydrogenation reaction, the hydrogenation catalyst is subjected to a sulfurization treatment, and the conditions of the sulfurization treatment include: a hydrogen pressure of 2.0 MPa to 3.5 MPa, a hydrogen-oil ratio of 300 to 500:1, a sulfurization temperature of 240°C to 350°C, and a volume space velocity of the sulfurized oil of 2 h -1 ~5h -1 The sulfide oil introduction time is 10h~30h.

15. The method according to claim 14, characterized in that The sulfided oil contains dimethyl disulfide.

16. The method according to claim 15, characterized in that Based on the total mass of the hydrogenation catalyst as a calculation basis, the content of dimethyl disulfide is 0.1wt%~5.0wt%.