Unsaturated hydrocarbon hydrogenation method for crude oil cracking process

Abstract

The present invention relates to the field of unsaturated hydrocarbon hydrogenation, and specifically discloses a method for hydrogenating unsaturated hydrocarbons for use in crude oil cracking processes. The method comprises two-stage catalytic hydrogenation, first desulfurization and first hydrogenation, followed by full hydrogenation under the action of a hydrogenation catalyst having a specific basic center. The basic center enables the hydrogenation catalyst to have a pyrrole adsorption in-situ infrared spectrum at 40°C, with a wavelength of 3200-3400 cm ‑1 The N-H bond stretching vibration absorption peak appears in the range of 3160-3420cm in the in-situ infrared spectrum of the hydrogenation catalyst after adsorbing pyrrole at 40 ° C and purging with nitrogen at 0 minutes and 15 minutes. ‑1 The ratio of the peak heights of the adsorption peaks within the range is greater than 5. The method of the present invention can achieve full hydrogenation of unsaturated hydrocarbons, remove organic sulfur, and solve the problems of the full hydrogenation reactor of C4 or / and C5 logistics being unable to operate for a long period of time and the impurities in the discharge exceeding the standard.

Description

Technical Field

[0001] The present invention relates to the field of unsaturated hydrocarbon hydrogenation, and in particular to an unsaturated hydrocarbon hydrogenation method for a crude oil cracking process. Background Art

[0002] Naphtha is the primary feedstock for steam cracking ethylene production in my country. Due to resource scarcity, significant fluctuations in international oil prices, and the continuous expansion of ethylene plant capacity, domestic cracking feedstock is facing a potential shortage. There is an urgent need to develop new cracking feedstock sources beyond naphtha to meet the needs of the growing ethylene industry. In the ethylene production process using naphtha steam cracking, the yield of C4 hydrocarbons can reach 20%-25% of the ethylene output. Aside from the extraction of butadiene and some butenes, the remaining C4 hydrocarbons are primarily used as fuel, resulting in a low chemical utilization rate. The C5 hydrocarbons, aside from the separation of dienes, have an even lower chemical utilization rate. Therefore, fully utilizing C4 and C5 resources, either by hydrogenating the mixed C4 and C5 fractions or the remaining C4 and C5 fractions after the extraction of dienes and some monoolefins, can convert the unsaturated C4 and C5 hydrocarbons into saturated C4 and C5 hydrocarbons, which can serve as a new source of cracking feedstock.

[0003] Using the alkanes from the hydrogenated C4 and C5 fractions as cracking feedstock not only broadens the source of cracking feedstock but also achieves the goal of increasing ethylene production without increasing the company's raw material consumption. This improves the utilization rate of C4 and C5, while reducing ethylene production costs, making it an effective means of improving the company's economic benefits. Due to its low olefin content, hydrogenated C4 alkanes can also be directly used as urban vehicle fuel, providing a new approach to processing by-product C4 hydrocarbons.

[0004] Palladium (Pd) supported catalysts have been widely used in the petrochemical industry as the best active component for hydrogenation of alkynes, dienes and monoolefins. Pd is dispersed on a suitable carrier through impregnation, metal ion vapor deposition, solvated metal atom impregnation, ion exchange and sol-gel methods. CN1229312C discloses a catalyst supported on alumina, with precious metal palladium or platinum as the main active component and metal additives, which is suitable for hydrogenation of C4 and C5 fractions of various compositions. It has the characteristics of high liquid space velocity and long life. It can be used at a reaction inlet temperature of 20-60°C, pressure of 2-5MPa and liquid space velocity of 1-30h -1 Under these conditions, the C4 alkane content in the product is greater than 99 wt%, and can be used as a high-quality cracking raw material and vehicle fuel. BASF has developed a C4 full hydrogenation catalyst with palladium as the active component and alumina as the carrier, with the commercial brand HO-40. The operating conditions of HO-40 are: reaction inlet temperature 20-150°C, reaction pressure 1-5 MPa, liquid space velocity 5-15h -1, the circulating feed rate is 5-25, and the butene content in the hydrogenated product is less than 1 (wt)%.

[0005] Logistics from crude oil cracking processes often contain organic sulfur, which affects the performance of catalysts in full hydrogenation reactors, causing catalyst deactivation and insufficient hydrogenation capacity. This places higher demands on the unsaturated hydrocarbon hydrogenation technology and catalyst performance of C4 and C5 logistics. In addition, the catalytic reaction in the unsaturated hydrogenation process generally adopts a lower liquid phase space velocity, which easily causes olefin polymerization and coking on the catalyst surface during the reaction. Coupled with the adsorption of organic sulfur, it is easy to shorten the catalyst operation cycle. It is necessary to provide a hydrogenation method for the hydrogenation of logistics from crude oil cracking processes and a Ni-ZnO catalyst, which can remove organic sulfur while ensuring hydrogenation activity and efficiency, ensure stable operation of the device, and extend the service life of the catalyst. Summary of the Invention

[0006] The purpose of the present invention is to address the problems in the crude oil steam cracking sequential separation process that trace organic sulfur can lead to rapid deactivation of hydrogenation catalysts, poor full hydrogenation to alkanes effect and short operating cycle. The present invention provides an unsaturated hydrocarbon hydrogenation method for the crude oil cracking process. The method can remove organic sulfur and effectively prevent polymerization and coking during the gas phase hydrogenation process through a two-stage gas phase hydrogenation method using two catalysts, thereby extending the operating cycle.

[0007] To achieve the above-mentioned object, the present invention provides a method for hydrogenating unsaturated hydrocarbons for use in a crude oil cracking process, the method comprising: mixing a stream from the crude oil cracking process with hydrogen, performing desulfurization and a first hydrogenation treatment in the presence of a Ni-ZnO catalyst, and performing a second hydrogenation treatment on the resulting material in the presence of a hydrogenation catalyst to convert the unsaturated hydrocarbons into corresponding alkanes;

[0008] The hydrogenation catalyst contains a basic center, wherein the basic center makes the hydrogenation catalyst test pyrrole adsorption in situ infrared spectrum at 40 ° C. 3200-3400 cm -1 Moreover, after the hydrogenation catalyst adsorbs pyrrole at 40 ° C, the in-situ infrared spectrum measured at 3160-3420 cm-1 with nitrogen purge for 0 minutes is as follows: -1 The peak height of the adsorption peak in the range is consistent with the peak at 3160-3420 cm in the in-situ infrared spectrum measured by nitrogen purge for 15 minutes. -1 The ratio of adsorption peak height within the range is greater than 5;

[0009] Among them, the flow from the crude oil cracking process contains C4-C5 unsaturated olefins and organic sulfur.

[0010] Preferably, the preparation method of the hydrogenation catalyst comprises: (1) loading palladium and an optional modifying component on a second carrier, drying and calcining to obtain an intermediate; (2) loading an alkaline compound on the intermediate, drying and optionally calcining to obtain the hydrogenation catalyst.

[0011] The method for full hydrogenation of unsaturated hydrocarbons provided by the present invention has a strong hydrogenation capacity, and the alkane content in the mixed stream after full hydrogenation is greater than 99.2 mol%. Under liquid-phase hydrogenation conditions, the method has a strong unsaturated hydrocarbon processing capacity. Combined with precise control of the alkalinity of the hydrogenation catalyst surface, it prevents polymerization and coking of unsaturated hydrocarbons during deep hydrogenation, thereby extending the service life of the unsaturated hydrocarbon full hydrogenation technology.

[0012] The hydrogenation catalyst provided by this invention is characterized by its in-situ infrared spectrum of pyrrole adsorption, ensuring that the catalyst surface has basic centers of specific basic strength. The presence of these basic centers is further confirmed by the change in the height of specific adsorption peaks in the spectrum during a 15-minute purge. The in-situ infrared analysis of the catalyst allows for easy quantification, ensuring that the catalyst possesses specific catalytic activity and selectivity.

[0013] The preferred preparation method for the hydrogenation catalyst provided by the present invention employs organic and / or inorganic basic compounds to provide effective basic centers in the catalyst, and quantitatively determines the strength of the basic centers through in-situ infrared analysis using pyrrole adsorption. This simple and easy preparation method obtains the basic centers required for the reaction, effectively enhancing the catalyst's hydrogenation capacity. It also prevents Pd accumulation on the catalyst surface and coking from the polymerization of alkynes and dienes, thereby extending the catalyst's lifespan.

[0014] The present invention addresses the problems of rapid deactivation of hydrogenation catalysts and poor effect of full hydrogenation to alkanes caused by trace organic sulfur in processes such as sequential separation, pre-depropanization and pre-deethanization hydrogenation corresponding to crude oil steam cracking, and designs a two-stage catalytic hydrogenation method. The method can achieve full hydrogenation of unsaturated hydrocarbons and remove trace organic sulfur under liquid phase conditions, thereby solving the problems of long-term operation of full hydrogenation reactors for mixed C4 and / or C5 streams in the main separation process corresponding to crude oil steam cracking and excessive impurities in the fuel gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The corresponding in-situ infrared spectrum of pyrrole adsorption of catalyst 1 prepared in Example 1 is shown.

[0016] Figure 2The in-situ infrared spectrum of pyrrole adsorption of catalyst 4 prepared in Example 4 over time is shown; in the spectrum, 0 min represents the infrared absorption curve at the end of nitrogen purge; 4 min, 6 min, and 10 min are the infrared absorption curves of pyrrole adsorption at the 4th, 6th, and 10th minutes; 25 min is the infrared absorption curve after 15 minutes of nitrogen purge at the end of pyrrole adsorption. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0018] The present invention provides a method for hydrogenating unsaturated hydrocarbons for use in a crude oil cracking process, the method comprising: mixing a stream from the crude oil cracking process with hydrogen, performing desulfurization and a first hydrogenation treatment in the presence of a Ni-ZnO catalyst, and performing a second hydrogenation treatment on the resulting material under the action of a hydrogenation catalyst to convert the unsaturated hydrocarbons into corresponding alkanes;

[0019] The hydrogenation catalyst contains a basic center, wherein the basic center makes the hydrogenation catalyst test pyrrole adsorption in situ infrared spectrum at 40 ° C. 3200-3400 cm -1 Moreover, after the hydrogenation catalyst adsorbs pyrrole at 40 ° C, the in-situ infrared spectrum measured at 3160-3420 cm-1 with nitrogen purge for 0 minutes is as follows: -1 The peak height of the adsorption peak in the range is consistent with the peak at 3160-3420 cm in the in-situ infrared spectrum measured by nitrogen purge for 15 minutes. -1 The ratio of adsorption peak height within the range is greater than 5;

[0020] Among them, the flow from the crude oil cracking process contains C4-C5 unsaturated olefins and organic sulfur.

[0021] The method described in the present invention is applicable to a stream from a crude oil steam cracking process, which can be from processes such as steam cracking, catalytic cracking, catalytic cracking, and hydrocracking. The stream can include a C4 fraction and / or a C5 fraction, specifically a C4 fraction, a C5 fraction, or a combination of a C4 fraction and a C5 fraction. The C4 fraction can include butanes (such as n-butane, isobutane, etc.), butenes (such as isobutene, 1-butene, and 2-butene, etc.), and butadiene (such as 1,3-butadiene). The C5 fraction can include pentane, pentadiene (such as isoprene, cyclopentadiene, and piperylene, etc.), and C5 monoolefins (such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, etc.). The stream may also include a small amount of C6 fraction.

[0022] Preferably, the C4-C5 unsaturated olefin is at least one selected from butene, butadiene, pentene and pentadiene.

[0023] By weight, the content of C4-C5 unsaturated olefins in the stream from the crude oil cracking process is 15-40 weight % (for example, it can be 15, 20, 25, 30, 35, 40 weight % and any range between any two values), preferably 22-32 weight %, and the content of organic sulfur is less than 50 ppm (for example, it can be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 ppm and less and any range between any two values), preferably 1-20 ppm.

[0024] For example, when the stream from the crude oil cracking process is mainly a C4 fraction, preferably, by weight, the content of butane in the stream is 70-75% by weight, the content of butene is 20-28 mol%, the content of butadiene is 2-5 mol%, and the content of organic sulfur is below 50 ppm.

[0025] For example, when the stream from the crude oil cracking process is mainly a C5 fraction, preferably, by weight, the pentane content in the stream is 70-75% by weight, the C5 monoolefin content is 20-28 mol%, the pentadiene content is 2-5 mol%, and the organic sulfur content is below 50 ppm.

[0026] The stream from the crude oil cracking process can be heat exchanged through a conventional heat exchange device and then enter a reactor (such as an adiabatic bed reactor) for desulfurization and a first hydrotreatment. It should be understood that the reactor is loaded with a Ni-ZnO catalyst.

[0027] Preferably, the conditions for desulfurization and the first hydrotreatment include: a reactor inlet temperature of 30-70°C (e.g., 30, 40, 50, 60, 70°C, and any range between any two values); a reaction pressure of 0.5 MPa-3 MPa (e.g., 0.5, 1, 1.5, 2, 2.5, 3 MPa, and any range between any two values); a gas phase space velocity of 5-90 h -1 (For example, it can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90h -1 and any range between any two values), the molar ratio of hydrogen to unsaturated hydrocarbon is 0.8-1.5 (for example, it can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 and any range between any two values).

[0028] The Ni-ZnO catalyst may be a supported catalyst or an unsupported catalyst, without any particular limitation.

[0029] If the Ni-ZnO catalyst is a supported catalyst, the supported Ni-ZnO catalyst comprises Ni, ZnO and a first carrier. Preferably, the Ni content in the supported Ni-ZnO catalyst is 2-20wt%, more preferably 8-10wt%; the ZnO content is 8-30wt%, more preferably 15-25wt%; and the content of the first carrier is 50-90wt%, more preferably 65-77wt%.

[0030] For example, the first support can be selected from at least one of aluminum oxide, titanium oxide, zirconium oxide, gallium oxide, silicon oxide, magnesium oxide, molecular sieves, zeolites, activated carbon, clay, bentonite, and polymer materials (such as polyacrylate, polystyrene, carbon supports, etc.). Its shape includes but is not limited to powder, granules, spheres, toothed spheres, Raschig rings, strips, cylinders, sheets, or clover leaves.

[0031] Preferably, the specific surface area of ​​the first carrier is 0.5-800m 2 / g, more preferably 4-200m 2 / g, more preferably 15-110m 2 / g.

[0032] When the catalyst is an unsupported catalyst, the Ni-ZnO catalyst does not contain a carrier. Preferably, the Ni content in the unsupported catalyst is 5-50wt% (for example, it can be 5, 8, 10, 15, 20, 30, 40, 50wt% and any range between any two values), more preferably 8-30wt%; the ZnO content is 50-95wt% (for example, it can be 50, 60, 70, 80, 90, 95wt% and any range between any two values), more preferably 70-92wt%.

[0033] The Ni-ZnO catalyst can be commercially available or homemade, and the preparation method can be conventional in the art. For example, an unsupported catalyst can be prepared by coprecipitation followed by drying and calcination; a supported catalyst can be prepared by impregnating a first support with Ni and Zn precursor compounds, followed by drying and calcination. It should be understood that the impregnation, drying, and calcination steps can be repeated multiple times to increase the loading.

[0034] The precursors of Ni and Zn can be selected from halogen compounds, nitric acid compounds, acetic acid compounds, carbonate compounds, oxalic acid compounds, acetic acid compounds, citric acid compounds, and the like.

[0035] Those skilled in the art can select a suitable method for preparation according to the circumstances, which will not be described in detail here. The temperature and time of drying and calcining can refer to the conditions of the hydrogenation catalyst.

[0036] The material after the Ni-ZnO catalyst can be subjected to a second hydrogenation in a conventional reactor to achieve full hydrogenation. For example, the second hydrogenation can be carried out in an adiabatic bed reactor.

[0037] Preferably, the second hydrogenation conditions are such that the alkane content in the material after the second hydrogenation is greater than 99.2 mol%.

[0038] Preferably, the conditions for the second hydrogenation include: an inlet temperature of 30-70°C (e.g., 30, 40, 50, 60, 70°C and any range between any two values); a reaction pressure of 0.5 MPa-3 MPa (e.g., 0.5, 1, 1.5, 2, 2.5, 3 MPa and any range between any two values); a gas phase space velocity of 10-80 h -1 (For example, it can be 10, 20, 30, 40, 50, 60, 70, 80h -1and any range between any two values), the molar ratio of hydrogen to unsaturated hydrocarbon is 0.8-5 (for example, it can be 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 and any range between any two values).

[0039] In the present invention, the pyrolyte adsorption in-situ infrared spectrum of the hydrogenation catalyst is measured by the following method:

[0040] a) placing a powdered catalyst sample in an infrared cell, vacuum-treating it, and then heating it to 350°C at a rate of 20°C / min;

[0041] b) keeping the temperature at 350°C for 2 h in a vacuum state, and then cooling to 40°C at a cooling rate of 20°C / min;

[0042] c) Maintaining the temperature at 40°C, introduce nitrogen gas for 30 minutes at a nitrogen flow rate of 5 mL / min;

[0043] d) maintaining the temperature at 40° C., introducing gaseous pyrrole for adsorption for 10 minutes at a gas flow rate of 5 mL / min, and recording the in situ infrared spectrum of the sample;

[0044] e) Maintaining the temperature at 40°C, purge with nitrogen at a flow rate of 5 mL / min for 30 minutes, and record the in situ infrared spectrum of the sample.

[0045] Before testing, the granular catalyst sample should be ground into powder and filled into the in-situ sample cell with the surface kept flat. The purpose of steps a to c is to remove water and impurities adsorbed on the catalyst surface.

[0046] In the pyrrole adsorption step (step d), the in-situ infrared spectrum of the sample can be recorded at different times as needed, for example, the in-situ infrared spectrum of the sample can be recorded at 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, and 10 minutes. In the in-situ infrared spectrum of pyrrole adsorption, 3160-3420 cm -1 The NH bond stretching vibration absorption peak appears in the range of 3160-3420cm, which corresponds to the base strength of the basic center on the catalyst surface. The higher the wave number of the peak position, the weaker the base strength of the basic center. -1 There are multiple NH bond stretching vibration absorption peaks in the range, indicating that the basic centers on the catalyst surface are diversified. The peak positions of pyrrole adsorption on different catalysts are quite different. Usually two or more peaks will overlap. In some cases, one peak will become the shoulder of another peak. In order to calculate the peak positions of each adsorption peak, the commonly used data processing software can be used to analyze the peak positions of 3160-3420cm -1 The absorption curve of the interval was fitted with peaks.

[0047] After purging with nitrogen, the intensity of the pyrrole infrared absorption peak gradually weakened. Spectrum 3160-3420cm after purging for 15 minutes -1 Absorption peak in the range 3160-3420cm and purge 0 minute spectrum -1 The peak height ratio of the absorption peaks within the range can be used to illustrate the adsorption capacity of the basic center on the catalyst surface for pyrrole, proving the existence of the basic center.

[0048] After the measurement, nitrogen purging can be maintained until the temperature drops to room temperature, with a nitrogen flow rate of 3-7 mL / min.

[0049] The hydrogenation catalyst is at 3200-3400 cm -1 (For example, it can be 3200, 3220, 3240, 3260, 3280, 3300, 3320, 3340, 3360, 3380, 3400cm -1 One or more NH bond stretching vibration absorption peaks may appear within the range of (and any range between any two values).

[0050] Preferably, the basic center allows the hydrogenation catalyst to have at least 3200-3300 cm -1 The NH bond stretching vibration absorption peak appears in the range.

[0051] Preferably, the basic center makes the hydrogenation catalyst absorb pyrrole at 40°C and then purge with nitrogen for 0 minutes, and the in-situ infrared spectrum of 3160-3420 cm -1 The peak height of the adsorption peak in the range is consistent with the peak at 3160-3420 cm in the in-situ infrared spectrum measured by nitrogen purge for 15 minutes. -1 The ratio of the adsorption peak height within the range is greater than 10.

[0052] In the present invention, preferably, the hydrogenation catalyst is a supported palladium catalyst, comprising a second support, palladium and an optional modifying component.

[0053] Preferably, the palladium content in the hydrogenation catalyst is 0.01-70 wt% of the weight of the second support, calculated as the metal element, for example, it can be 0.01, 0.02, 0.05, 0.1, 0.5, 1, 5, 10, 20, 40, 70 wt% and any range between any two values, more preferably 0.01-20 wt%, and even more preferably 0.02-6 wt%.

[0054] The palladium on the catalyst surface may exist in the form of an oxidized state, a simple state, other palladium compound forms, or a mixture of two or more thereof.

[0055] The hydrogenation catalyst of the present invention may be a single palladium supported catalyst or a composite catalyst, loaded with palladium and a modifying component, wherein the modifying component may be a conventional modifying component in the art, for example, it may be selected from at least one of Bi, Sb, Pb, Sn, Y, Zn, W, Mn, Si, Group VIII elements other than palladium (for example, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt), alkali metal elements (for example, Na, K), alkaline earth metal elements (for example, Mg, Ca, Sr, Ba), Group IIIA elements (for example, Ga, In, Tl), Group IB elements (for example, Cu, Ag, Au), rare earth elements (for example, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu) and halogen elements (for example, F, Cl, Br, I), more preferably selected from at least one of Cu, Zn, Ga, In, Cs, Y, Fe, Ag, Ni and Au. The modified component can be loaded on the second carrier together with Pd as a co-active component, or can be used as a modifier of the second carrier and uniformly distributed in the second carrier.

[0056] Preferably, the content of the modifying component in the hydrogenation catalyst, calculated as the metal element, is 0-20 wt% of the weight of the second support, for example, 0, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20 wt%, and any range consisting of any two values ​​therebetween. The modifying component can be co-loaded on the second support with palladium as a co-active component, or can be uniformly distributed on the second support as a modifier for the second support. Preferably, the modifying component is co-loaded on the second support with palladium as a co-active component.

[0057] The second carrier of the catalyst can be selected from at least one of aluminum oxide, titanium oxide, zirconium oxide, gallium oxide, silicon oxide, magnesium oxide, molecular sieves, zeolites, activated carbon, clay, bentonite and polymer materials (such as polyacrylates, polystyrene, carbon carriers, etc.).

[0058] The shape of the second carrier includes but is not limited to powder, granular, spherical, toothed ball, Raschig ring, strip, cylindrical, sheet or clover etc. Preferably, the specific surface area of ​​the second carrier is 0.5-800m 2 / g, preferably 4-200m 2 / g, more preferably 15-110m 2 / g.

[0059] Preferably, the preparation method of the hydrogenation catalyst comprises: (1) loading palladium and an optional modifying component on a second carrier, drying and calcining to obtain an intermediate; (2) loading an alkaline compound on the intermediate, drying and optionally calcining to obtain the hydrogenation catalyst.

[0060] In step (1), preferably, palladium is supported in the form of a solution containing a precursor of palladium, and the modifying component is supported in the form of a solution containing a precursor of the modifying component.

[0061] The palladium and modifying component precursors can be pre-formulated as a solution and loaded onto the second support by spraying or impregnation. When the catalyst includes a modifying component, such as when it serves as a co-activating component, it can be loaded onto the second support alone or simultaneously with the palladium. If the modifying component serves as a modifier for the second support, it can be added during the preparation of the second support.

[0062] The palladium precursor can be a conventional acid or base or water-soluble substance in the art, such as one or more selected from palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, palladium oxide and palladium metal organic compounds (such as palladium pivalate, octaethylporphyrin palladium, trimethylpalladium acetate, palladium trifluoroacetate, etc.).

[0063] The content of the palladium precursor in the solution containing the palladium precursor can be selected within a wide range. For example, the content of the palladium precursor in the solution containing the palladium precursor is 1-200 g / L, for example, it can be 1, 10, 20, 50, 100, 200 g / L and any range between any two values.

[0064] Preferably, the amount of palladium used, calculated as the metal element, is such that the palladium content in the hydrogenation catalyst is 0.01-70 wt % of the weight of the second support, for example, 0.01, 0.02, 0.05, 0.1, 0.5, 1, 5, 10, 20, 40, 70 wt % and any range between any two values, more preferably 0.01-20 wt %, further preferably 0.02-6 wt %.

[0065] Preferably, the precursor of the modifying component is selected from at least one of a modifying component halide (such as chloride, bromide, iodide), nitrate, acetate, carbonate, sulfate, hydroxide, ammonium, and a metal organic compound (such as citrate, oxalate, etc.). Specific compounds are known to those skilled in the art and are not listed here.

[0066] The content of the precursor of the modifying component in the solution containing the precursor of the modifying component can be selected within a wide range. For example, the content of the precursor of the modifying component in the solution containing the precursor of the modifying component is 0.1-400 g / L, for example, it can be 0.1, 1, 10, 20, 50, 100, 200, 300, 400 g / L and any range between any two values.

[0067] Preferably, the amount of the modifying component is such that, calculated as the metal element, the content of the modifying component in the hydrogenation catalyst is 0-20 wt % of the weight of the second support, for example, it can be 0, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20 wt % and any range between any two values.

[0068] The solvents in the solution of the precursor containing palladium and the solution of the precursor containing the modifying component can each independently be water, diethyl ether, ethanol, isobutanol, and the like.

[0069] In the present invention, the loading method may be a conventional method in the art, for example, the loading method may be a spraying method or an immersion method, and the specific operation will not be described in detail.

[0070] Preferably, the amount of the basic compound is 0.1-25 wt% compared to the weight of the second carrier, for example, 0.1, 0.5, 1, 2, 4, 6, 8, 10, 15, 20, 25 wt% and any range between any two values.

[0071] In step (2), the basic compound is preferably loaded in the form of a solution containing the basic compound. The basic compound may be an inorganic basic compound and / or an organic basic compound. The basic compound is a weakly basic compound.

[0072] Preferably, the organic alkaline compound is selected from at least one of organic amines (such as aliphatic amines, alcoholamines, amides, aromatic amines), pyridine compounds, alkali metal alkoxides and alkali metal salts, and more preferably selected from at least one of dimethylamine, triethylamine, acetamide, trifluoroacetamide, aniline, pyridine, 4-dimethylaminopyridine, triethanolamine, triethylenediamine, tetramethylethylenediamine, N,N-diisopropylethylamine, N-methylmorpholine, sodium methoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide and n-butyllithium.

[0073] Preferably, the inorganic alkaline compound is selected from at least one of ammonia, halides (such as KF, NaF, lithium chloride), citrates (such as sodium citrate or potassium citrate), oxalates (such as sodium oxalate, potassium oxalate), acetates (such as sodium acetate, potassium acetate), bicarbonates (such as sodium bicarbonate, carbonate) and carbonates (such as sodium carbonate, potassium carbonate), preferably at least one of KF, lithium chloride, potassium acetate, sodium bicarbonate and sodium citrate.

[0074] In a preferred embodiment of the present invention, the basic compound is at least one selected from acetate, carbonate, tetramethylethylenediamine and 4-dimethylaminopyridine.

[0075] The solvent in the solution containing the alkaline compound can be any solution that can dissolve the alkaline compound, and is preferably selected from at least one of water, methanol, ethanol, ether, acetone, tetrahydrofuran and N,N-dimethylformamide.

[0076] Preferably, the content of the alkaline compound in the solution containing the alkaline compound is 0.1-70 wt %, for example, it can be 0.1, 0.5, 1, 5, 10, 20, 30, 40, 70 wt % and any range between any two values.

[0077] Preferably, the amount of the basic compound is 0.1-10 wt % compared to the weight of the second carrier, for example, 0.1, 0.5, 1, 5, 10 wt % and any range between any two values.

[0078] In a preferred embodiment of the present invention, the method comprises: (1) loading palladium onto a second carrier, drying and calcining the carrier to obtain an intermediate; and (2) loading a basic compound onto the intermediate, drying the intermediate and optionally calcining the intermediate to obtain a catalyst.

[0079] In another preferred embodiment of the present invention, the method comprises: (1) loading palladium and a modifying component onto a second carrier, drying and calcining the carrier to obtain an intermediate; and (2) loading an alkaline compound onto the intermediate, drying the intermediate and optionally calcining the intermediate to obtain a catalyst.

[0080] In another preferred embodiment of the present invention, the method comprises: (1) loading a first modifying component onto a second carrier, drying and calcining the carrier to obtain a modified carrier; loading palladium and an optional second modifying component onto the modified carrier, drying and calcining the carrier to obtain an intermediate; and (2) loading an alkaline compound onto the intermediate, drying and optionally calcining the intermediate to obtain a catalyst.

[0081] In steps (1) and (2), when preparing the intermediate, modified support, or catalyst, the drying temperature can be independently 60-180°C, for example, 60, 80, 120, 160, 180°C, and any range between any two values. The drying time can be independently 1-48 hours, for example, 1, 5, 10, 20, 30, 40, 48 hours, and any range between any two values. It should be understood that the drying can be performed at least once, and the drying conditions can be different each time.

[0082] In step (1), the calcination temperature may be 300-1500°C, for example, 300, 400, 600, 800, 1000, 1200, 1400, 1500°C, and any range between any two values. Preferably, in the process of preparing the intermediate, the calcination temperature is 600-1500°C, for example, 600, 800, 1000, 1200, 1400, 1500°C, and any range between any two values. In the process of preparing the modified support, the calcination temperature is preferably 300-1000°C, for example, 300, 400, 600, 800, 1000°C, and any range between any two values.

[0083] In step (2), the calcination temperature is preferably 250-500°C, for example, it can be 200, 250, 300, 350, 400, 450, 500°C and any range between any two values.

[0084] In steps (1) and (2), the calcination time can be independently 2-24 h, for example, 2, 4, 8, 12, 16, 20, 24 h and any range between any two values.

[0085] In steps (1) and (2) of the preparation method of the present invention, the drying and calcining can be independently carried out in an air atmosphere or under vacuum, preferably independently carried out in an air atmosphere.

[0086] The present invention will be described in detail below through examples.

[0087] Unless otherwise specified, in the examples and comparative examples, the reagents used are all reagents commonly used in the art, and the methods adopted are all conventional methods in the art.

[0088] The Al2O3 carriers used below were purchased from Sinopec Catalyst (Beijing) Co., Ltd., with a specific surface area of ​​50-60m 2 / g.

[0089] Preparation Example 1

[0090] This preparation example is used to provide a method for preparing a Ni-ZnO supported catalyst.

[0091] Prepare 500 ml of a Ni(NO3)2 aqueous solution containing 20 g of Ni and 50 g of Zn(NO3)2, impregnate 500 g of a spherical carrier Al2O3 into the solution, dry at 150°C, and calcine at 650°C to obtain intermediate 1.

[0092] Prepare 500 ml of a Ni(NO3)2 aqueous solution containing 20 g of Ni and 70 g of Zn in Zn(NO3)2, immerse the intermediate 1 in the solution, dry at 150°C, and calcine at 650°C to obtain the intermediate 2;

[0093] Prepare 500 ml of a Ni(NO3)2 aqueous solution containing 10 g Ni and 80 g Zn. Immerse the intermediate 2 in the solution, dry it at 150°C, and calcine it at 650°C to obtain a Ni-ZnO / Al2O3 supported catalyst, which is designated as catalyst S.

[0094] Example 1

[0095] Prepare 400 mL of ether solution containing 1.2 g of Pd in ​​Pd(Ac)2 solution and 5.0 g of Cs in Cs(Ac), impregnate 500 g of cloverleaf-shaped support Al2O3 into the solution, dry at 80°C for 48 h, and calcine at 450°C for 8 h to obtain Pd-Cs / Al2O3 intermediate;

[0096] 400 mL of K(Ac) ethanol solution containing 2.0 g of K was prepared, and the Pd-Cs / Al2O3 intermediate was impregnated in the solution and dried at 80°C for 30 h to obtain catalyst 1.

[0097] Example 2

[0098] 400 mL of an ethanol solution of copper acetate containing 3.1 g of Cu was prepared, 500 g of a toothed spherical carrier Al2O3 was impregnated in the solution, dried at 75°C for 40 h, and calcined at 1100°C for 20 h to obtain a Cu-modified carrier Al2O3.

[0099] Prepare 300 mL of an aqueous solution of Pd(NO3)2 containing 0.5 g of Pd, impregnate the Cu-modified support Al2O3 in the solution, dry at 105°C for 6 h, and calcine at 700°C for 4 h to obtain a Pd-Cu / Al2O3 intermediate;

[0100] Prepare 250 mL of an aqueous solution containing 50 mL of tetramethylethylenediamine, immerse the Pd-Cu / Al2O3 intermediate in the solution, and dry at 75°C for 20 h to obtain catalyst 2.

[0101] Example 3

[0102] Prepare 265 mL of an isobutanol solution of HAuCl4 containing 0.5 g of Au, impregnate 500 g of a columnar Al2O3 support into the solution, dry at 110°C for 2 h, and calcine at 1270°C for 6 h to obtain an Au-modified Al2O3 support;

[0103] Prepare 300 mL of an aqueous solution of Pd(NO3)2 containing 4.8 g of Pd and Ga(NO3)3 containing 0.8 g of Ga, impregnate the Au-modified support Al2O3 in the solution, dry at 140°C for 12 h, and calcine at 820°C for 14 h to obtain a Pd-Ga-Au / Al2O3 intermediate;

[0104] 300 mL of an acetone solution containing 110 mL of 4-dimethylaminopyridine (DMAP) was prepared, the Pd-Ga-Au / Al2O3 intermediate was immersed in the solution, and dried at 165°C for 20 h to obtain catalyst 3.

[0105] Example 4

[0106] Prepare 250 mL of an aqueous solution of [(NH4)2Pd]Cl4 containing 0.3 g of Pd, [(NH4)2Ag]Cl3 containing 0.5 g of Ag, and ZnCl2 containing 1.1 g of Zn. Impregnate 500 g of a spherical Al2O3 support in the solution, dry at 105°C for 12 h, and calcine at 650°C for 15 h to obtain a Pd-Zn-Ag / Al2O3 intermediate.

[0107] 250 mL of an aqueous solution of KF containing 1.0 g of K was prepared, and the Pd-Zn-Ag / Al2O3 intermediate was immersed in the solution, dried at 160°C for 4 h, and calcined at 300°C for 4 h to obtain catalyst 4.

[0108] Example 5

[0109] Prepare 180 mL of a PdSO4 aqueous solution containing 2.5 g of Pd, spray the solution onto 500 g of a spherical Al2O3 carrier, dry at 140°C for 12 h, and calcine at 620°C for 10 h to obtain a Pd / Al2O3 intermediate;

[0110] 180 mL of an aqueous solution of NaHCO 3 containing 0.6 g of Na element was prepared and sprayed onto the Pd / Al 2 O 3 intermediate. The mixture was dried at 125° C. for 10 h and calcined at 445° C. for 16 h to obtain catalyst 5.

[0111] Comparative Example 1

[0112] Prepare 400 mL of an aqueous solution of NaHCO3 containing 0.6 g of Na element, impregnate 500 g of a spherical carrier Al2O3 into the solution, dry at 125°C for 10 h, and calcine at 1050°C for 20 h to obtain a Na / Al2O3 intermediate.

[0113] 180 mL of a PdSO4 aqueous solution containing 2.5 g of Pd was prepared, and the solution was sprayed onto 500 g of a spherical carrier Al2O3. The solution was dried at 140°C for 12 h, and calcined at 620°C for 10 h to obtain catalyst D1.

[0114] Test Example 1

[0115] This test example is used to illustrate the in situ pyrrole adsorption infrared spectroscopy analysis of hydrogenation catalysts.

[0116] The catalysts prepared in the examples and comparative examples were tested for pyrrole adsorption using a pyrrole in situ infrared analyzer (Thermo Nicolet 380). About 10 mg of powder sample was pressed into a thin sheet, fixed in an infrared cell, and first vacuum-purified (400°C, 1×10 -3 Pa) for 3 hours, cooled to 40°C, and the spectrum was scanned as background. The method for determining the in-situ infrared spectrum of pyrolyte adsorption of the catalyst is as follows:

[0117] a) placing a powdered catalyst sample in an infrared cell, vacuum-treating it, and then heating it to 350°C at a rate of 20°C / min;

[0118] b) maintaining the temperature at 350°C for 2 hours in a vacuum state, and then cooling the temperature to 40°C at a cooling rate of 20°C / min;

[0119] c) Maintaining the temperature at 40°C, introduce nitrogen gas for 30 minutes at a nitrogen flow rate of 5 mL / min;

[0120] d) Maintaining the temperature at 40°C, introduce gaseous pyrrole for 10 minutes at a gas flow rate of 5 mL / min, and record the sample's concentration at 1000-4000 cm-1 at 2, 4, 6, 8, and 10 minutes after the introduction of gaseous pyrrole. -1 In situ infrared spectra in wavenumber regions;

[0121] e) Maintaining the temperature at 40°C, purge with nitrogen at a flow rate of 5 mL / min for 30 minutes;

[0122] f) Maintain nitrogen purge until the temperature drops to room temperature with a nitrogen flow rate of 5 mL / min.

[0123] in, Figure 1 The corresponding in-situ infrared spectrum of pyrrole adsorption of catalyst 1 prepared in Example 1 is shown.

[0124] Figure 2 The in situ infrared spectrum of pyrrole adsorption over time for catalyst 4 is shown. In the spectrum, 0 min represents the infrared absorption curve at the end of nitrogen purge; 4 min, 6 min, and 10 min represent the infrared absorption curves at the 4th, 6th, and 10th minutes of pyrrole adsorption; and 25 min represents the infrared absorption curve after the end of pyrrole adsorption and a 15-minute nitrogen purge.

[0125] The in situ infrared spectrum of pyrrole adsorption was analyzed, and the results are shown in Table 1. Table 1 shows the infrared spectrum of 3160-3420 cm at 10 minutes. -1 Within the range, the peak positions of the infrared absorption peaks of pyrrole of the catalysts prepared in the examples and comparative examples, as well as the peak height ratio H 10min / H 25min , where H 10min 3160-3420 cm-1 at 10 min of pyrrole adsorption -1 The highest peak height within the range (when there are two or more peaks, the highest peak height is used for calculation), H 25min 3160-3420 cm-1 at the end of pyrrole adsorption and nitrogen purge for 15 min -1 The highest peak height within the range (when there are two or more peaks, the highest peak height is used for calculation).

[0126] Table 1

[0127]

[0128] As shown in Table 1, the infrared peak position of pyrrole adsorption of the catalyst prepared by the method of the embodiment of the present invention is at a wavelength of 3200-3400 cm -1 The pyrrole adsorption infrared peak positions of the catalysts prepared in the comparative example are all greater than 3410 cm -1 After pyrrole adsorption was completed and nitrogen was used for purging, the pyrrole adsorbed on the catalyst surface was rapidly desorbed, and the peak height ratios of each catalyst were all above 10, indicating that each peak position in Table 1 corresponds to a basic center.

[0129] Test Example 2

[0130] This test case is used to illustrate the effect evaluation of hydrogenation of sulfur-containing C4 stream in crude oil cracking process.

[0131] The full hydrogenation of unsaturated hydrocarbons in a C4 stream obtained from crude oil steam cracking separation is carried out in a two-stage adiabatic fixed-bed reactor. The reactor inlet feedstock is a C4 fraction stream with a composition (mass fraction) of 24.7% butene, 3.9% butadiene, 25 ppm COS, and the balance butane. The space velocity of the first and second adiabatic bed reactors is 50 h / min. -1 , pressure 1.0 MPa; the first-stage reactor was filled with the catalyst S prepared in Preparation Example 1, the amount of hydrogen at the reactor inlet was adjusted to a molar ratio of hydrogen to unsaturated hydrocarbons of 0.8-1.5, and the reactor inlet temperature was 40°C; the second-stage reactor was filled with a hydrogenation catalyst (as shown in Table 2), the amount of hydrogen at the reactor inlet was adjusted to a molar ratio of hydrogen to unsaturated hydrocarbons of 1.0-2.0, and the reactor inlet temperature was 45°C.

[0132] The unsaturated hydrocarbon content at the outlet was controlled to be less than 8000 ppm, and the alkane content (mol%), outlet COS content and operating cycle (h) of each catalyst after hydrogenation were measured. The results are shown in Table 2.

[0133] The operating cycle refers to the time the system can operate when the total content of unsaturated hydrocarbons at the outlet of the second-stage reactor is controlled below 8000 ppm.

[0134] Table 2

[0135] Hydrogenation catalyst Alkane content after hydrogenation (mol%) Export COS (ppb) Operation cycle (h) 1 99.91 15 787 2 99.64 25 782 3 99.83 20 737 4 99.37 27 685 5 99.26 18 624 D1 90.56 408 348

[0136] Table 2 shows the results of the full hydrogenation of unsaturated hydrocarbons in the crude oil cracking and separation process. The catalyst prepared in Example exhibited an alkane content greater than 99.2 mol% before and after hydrogenation, an outlet COS of less than 30 ppb, and an operating cycle exceeding 600 hours. The catalyst prepared in Example had a longer operating life than the catalyst prepared in Comparative Example 1, demonstrating superior full hydrogenation performance. This demonstrates that the full hydrogenation method for unsaturated hydrocarbons in the crude oil cracking and separation process described in this invention can effectively remove unsaturated hydrocarbons and trace organic sulfur, achieving long-term stable operation.

[0137] Test Example 3

[0138] This test example is used to illustrate the evaluation of the anti-sulfur effect of the catalyst.

[0139] The operation was carried out according to the method of Test Example 2, except that the first-stage reactor used the same hydrogenation catalyst as that loaded in the second-stage reactor instead of catalyst S.

[0140] The test results are shown in Table 3.

[0141] Table 3

[0142]

[0143]

[0144] From the results given in Table 3, it can be seen that when the total content of unsaturated hydrocarbons is controlled below 10,000 ppm, the catalyst prepared in the example has a longer operating time than the catalyst prepared in the comparative example, a higher alkane content after hydrogenation, and a lower outlet COS content, indicating that the catalyst having a specific basic center in the present invention has better sulfur resistance.

[0145] Comparison of the data in Table 2 and Table 3 shows that desulfurization by the Ni-ZnO catalyst can effectively extend the operating time and improve the catalytic effect of the hydrogenation catalyst.

[0146] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for hydrogenating unsaturated hydrocarbons for use in a crude oil cracking process, characterized in that: The method comprises: mixing a stream from a crude oil cracking process with hydrogen, performing desulfurization and a first hydrogenation treatment in the presence of a Ni-ZnO catalyst, and performing a second hydrogenation treatment on the resulting material in the presence of a hydrogenation catalyst to convert unsaturated hydrocarbons into corresponding alkanes; The hydrogenation catalyst is a supported palladium catalyst, comprising a second support, palladium and an optional modifying component; the hydrogenation catalyst contains a basic center, wherein the basic center enables the hydrogenation catalyst to have a pyrrole adsorption in-situ infrared spectrum at 40°C, 3200-3400 cm -1 Moreover, after the hydrogenation catalyst adsorbed pyrrole at 40 ° C, the in-situ infrared spectrum measured at 3160-3420 cm was purged with nitrogen for 0 minutes. -1 The peak height of the adsorption peak in the range is consistent with the peak at 3160-3420 cm in the in-situ infrared spectrum measured by nitrogen purge for 15 minutes. -1 The ratio of adsorption peak height within the range is greater than 5; Among them, the stream from the crude oil cracking process contains C4-C5 unsaturated olefins and organic sulfur; The in-situ infrared spectrum of pyrolysis adsorption of the hydrogenation catalyst is measured by the following method: a) A powdered hydrogenation catalyst sample was placed in an infrared cell, vacuum treated, and then heated to 350°C at a rate of 20°C / min. b) Keep at 350°C for 2 h in a vacuum state, then cool to 40°C at a cooling rate of 20°C / min; c) Maintain the temperature at 40°C and introduce nitrogen purge for 30 minutes at a nitrogen flow rate of 5 mL / min; d) Maintaining the temperature at 40°C, introduce gaseous pyrrole for adsorption for 10 minutes at a gas flow rate of 5 mL / min, and record the in situ infrared spectrum of the sample; e) Maintaining the temperature at 40°C, switch to nitrogen purge for 30 minutes at a nitrogen flow rate of 5 mL / min, and record the in situ FTIR spectrum of the sample.

2. The method according to claim 1, wherein The stream from the crude oil cracking process has a C4-C5 unsaturated olefin content of 15-40% by weight and an organic sulfur content of less than 50 ppm.

3. The method according to claim 2, wherein: The stream from the crude oil cracking process has a C4-C5 unsaturated olefin content of 22-32% by weight and an organic sulfur content of 1-20 ppm; and / or, the organic sulfur is selected from at least one of COS, CS2, mercaptans and thioethers; And / or, the C4-C5 unsaturated olefin is at least one selected from butene, butadiene, pentene and pentadiene.

4. The method according to claim 1, wherein Desulfurization and first hydrotreatment are carried out in an adiabatic bed reactor.

5. The method according to claim 4, wherein The conditions for desulfurization and the first hydrotreatment include: reactor inlet temperature of 30-70°C, reaction pressure of 0.5MPa-3MPa; gas phase space velocity of 5-90h -1 ; The molar ratio of hydrogen to unsaturated hydrocarbon is 0.8-1.

5.

6. The method according to claim 1, wherein The Ni-ZnO catalyst is a supported Ni-ZnO catalyst and / or an unsupported Ni-ZnO catalyst; The supported Ni-ZnO catalyst comprises Ni, ZnO and a first carrier, wherein the content of Ni in the supported Ni-ZnO catalyst is 2-20wt%, the content of ZnO is 8-30wt%, and the content of the first carrier is 50-90wt%; The content of Ni in the non-supported Ni-ZnO catalyst is 5-50wt%, and the content of ZnO is 50-95wt%.

7. The method according to claim 6, wherein: In the supported Ni-ZnO catalyst, the content of Ni is 8-10wt%, the content of ZnO is 15-25wt%, and the content of the first carrier is 65-77wt%; And / or, the content of Ni in the unsupported Ni-ZnO catalyst is 8-30 wt %, and the content of ZnO is 70-92 wt %.

8. The method according to claim 1, wherein The second hydrogenation is carried out in an adiabatic bed reactor.

9. The method according to claim 8, wherein The conditions of the second hydrogenation are such that the alkane content in the material after the second hydrogenation is greater than 99.2 mol%.

10. The method according to claim 9, wherein: The conditions of the second hydrogenation include: inlet temperature of 30-70°C; reaction pressure of 0.5MPa-3MPa; gas phase space velocity of 10-80h -1 , the molar ratio of hydrogen to unsaturated hydrocarbon is 0.8-5.

11. The method according to claim 1, wherein The basic center makes the hydrogenation catalyst have a pyrrole adsorption in-situ infrared spectrum at 3200-3300 cm -1 NH bond stretching vibration absorption peak appears in the range; and / or The basic center allows the hydrogenation catalyst to adsorb pyrrole at 40°C, and then nitrogen is used to purge for 0 minutes. The in-situ infrared spectrum at 3160-3420 cm -1 The peak height of the adsorption peak in the range is consistent with the peak at 3160-3420 cm in the in-situ infrared spectrum measured by nitrogen purge for 15 minutes. -1 The ratio of the adsorption peak height within the range is greater than 10.

12. The method according to any one of claims 1 to 11, wherein: Calculated as an element, the content of palladium in the hydrogenation catalyst is 0.01-70 wt% of the weight of the second carrier, and the content of the modifying component is 0-20 wt% of the weight of the second carrier.

13. The method according to claim 12, wherein: Calculated as an element, the content of palladium in the hydrogenation catalyst is 0.01-20 wt % of the weight of the second support; and / or, the second carrier is selected from at least one of aluminum oxide, titanium oxide, zirconium oxide, gallium oxide, silicon oxide, magnesium oxide, molecular sieves, activated carbon, clay and polymer materials; And / or, the modifying component is selected from at least one of Bi, Sb, Pb, Sn, Y, Zn, W, Mn, Si, Group VIII elements other than palladium, alkali metal elements, alkaline earth metal elements, Group IIIA elements, Group IB elements, rare earth elements and halogen elements.

14. The method according to claim 13, wherein Calculated as an element, the content of palladium in the hydrogenation catalyst is 0.02-6 wt % of the weight of the second support; And / or, the modifying component is selected from at least one of Cu, Zn, Ga, In, Cs, Y, Fe, Ag, Ni and Au.

15. The method according to claim 12, wherein: The preparation method of the hydrogenation catalyst comprises: (1) loading palladium and an optional modifying component on a second carrier, drying and calcining the carrier to obtain an intermediate; and (2) loading an alkaline compound on the intermediate, drying and optionally calcining the intermediate to obtain the hydrogenation catalyst.

16. The method according to claim 15, wherein The palladium is loaded in the form of a solution containing a palladium precursor, the modifying component is loaded in the form of a solution containing a modifying component precursor; the basic compound is loaded in the form of a solution containing the basic compound; and / or, the amount of palladium used, calculated as the element, is such that the palladium content in the hydrogenation catalyst is 0.01-70 wt % of the weight of the second support; and / or, the modifying component is used in an amount such that the content of the modifying component in the hydrogenation catalyst is 0-20 wt % of the weight of the second support, calculated as the element; And / or, compared to the weight of the second carrier, the amount of the basic compound is 0.1-25 wt %.

17. The method according to claim 16, wherein: Calculated as an element, the amount of palladium used is such that the palladium content in the hydrogenation catalyst is 0.01-20 wt % of the weight of the second support.

18. The method according to claim 17, wherein Calculated as an element, the amount of palladium used is such that the palladium content in the hydrogenation catalyst is 0.02-6 wt % of the weight of the second support.

19. The method according to claim 18, wherein The palladium precursor is selected from at least one of palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, palladium oxide and a metal organic compound of palladium; and / or The precursor of the modifying component is selected from at least one of a halide, a nitrate, an acetate, a carbonate, a sulfate, a hydroxide, an ammonium compound and a metal organic compound of the modifying component; and / or The alkaline compound is at least one of ammonia water, organic amine, pyridine compound and alkali metal salt.

20. The method according to claim 15, wherein The alkaline compound is selected from at least one of dimethylamine, triethylamine, acetamide, trifluoroacetamide, aniline, pyridine, 4-dimethylaminopyridine, triethanolamine, triethylenediamine, tetramethylethylenediamine, N,N-diisopropylethylamine, N-methylmorpholine, sodium methoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide, n-butyllithium, halides, citrates, oxalates, acetates, bicarbonates and carbonates.

21. The method according to claim 20, wherein The alkaline compound is selected from at least one of acetate, carbonate, tetramethylethylenediamine and 4-dimethylaminopyridine.

22. The method according to claim 16, wherein The solvent in the solution containing the basic compound is at least one selected from water, methanol, ethanol, ether, acetone, tetrahydrofuran and N,N-dimethylformamide.

23. The method according to claim 22, wherein The content of the alkaline compound in the alkaline compound-containing solution is 0.1-70 wt %.

24. The method according to any one of claims 15 to 23, wherein: In step (1), the drying conditions include: temperature of 60-180°C; time of 1-48h; and / or The calcination temperature is 300-1500°C; the calcination time is 2-24h; and / or In step (2), the drying temperature is 60-180°C and the drying time is 1-48 hours; and / or The calcination temperature is 250-500° C. and the calcination time is 2-24 hours.

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