Composite catalyst as well as preparation method and application thereof

Abstract

The invention relates to a composite catalyst as well as a preparation method and application thereof. The composite catalyst comprises a metal organic ligand catalyst and a molecular sieve catalyst, the metal organic ligand catalyst comprises an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is one or more of VB group metal, VIB group metal, VIII group metal, IB group metal and IIB group metal; the organic ligand comprises alkyl and a coordination group; the molecular sieve catalyst comprises a molecular sieve active component. The composite catalyst has high hydrogenation activity, when the composite catalyst is used for hydrogenation of oil products, the metal organic ligand catalyst provides a hydrogenation function, the molecular sieve catalyst provides an acidic function, generation of carbocations is promoted, cracking reaction of the oil products is effectively improved, hydrogen consumption of a reaction system is reduced, and it can be guaranteed that the product has lower sulfur and nitrogen content.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical engineering, and in particular to a composite catalyst and a preparation method and application thereof. Background Art

[0002] Hydrofining of petroleum products, including hydrodesulfurization, denitrogenation, and demetallization, has always been an important part of the petrochemical industry. With increasingly stringent environmental regulations and the rapid economic development, the demand for light oil and gas and chemical raw materials has grown rapidly, and it is becoming increasingly important to develop catalysts that can efficiently process heavy raw materials. Traditional hydrofining catalysts are fixed-bed supported catalysts, which are usually composed of active metals and carriers. The active metals usually have hydrogenation activity, and the carrier is alumina or a mixture of alumina and other oxides (such as ZrO2, MgO, etc.), which can provide the required acidity for cracking reactions. Supported catalysts have become the catalysts with the largest number of industrial applications and the widest range due to their high catalytic activity, strong mechanical strength, and mature process technology. However, as the quality of crude oil becomes increasingly poor, environmental protection and downstream devices have more stringent requirements for oil raw materials. Supported catalysts are in urgent need of upgrading and replacement due to their low diffusion and mass transfer efficiency and easy coking and deactivation of catalysts. The dispersed catalyst used in the slurry bed process has the characteristics of oil solubility, nano-size and high hydrogenation activity. It can overcome steric hindrance, efficiently convert heavy components, and avoid problems such as short operation cycle caused by coking and scaling. At the same time, due to the quasi-homogeneous and high mass and heat transfer efficiency of the slurry bed processing system, it has a high tolerance for solid content, and the reactor has a small temperature difference and can be operated at high temperature. Therefore, it is regarded as an effective way to hydrogenate heavy raw oil products, especially inferior raw materials. However, since the slurry bed catalyst is generally converted from the precursor online in situ to an active phase with a sulfide characteristic structure, it usually does not have an acidic function. Therefore, in the slurry bed hydrogenation system, hydrogenation thermal cracking is generally the main method. Different from the carbon cation mechanism of catalytic cracking, thermal cracking is usually composed of the initiation, transfer, and termination of free radicals. It has the characteristics of high reaction temperature, low activity, and high randomness. Therefore, many researchers use the combination of the two catalysts to process petroleum products.

[0003] CN103842077A discloses a catalytic system for heavy oil hydroconversion, which comprises a first catalyst having a hydrogenation function and composed of one or more sulfides of metals of Group VIB and / or Group VIII, and a second catalyst having a cracking function and composed of amorphous aluminosilicate and / or crystalline aluminosilicate and / or alumina.

[0004] CN103228355A discloses a dual catalytic system used in an ebullating bed reactor, comprising two different catalysts with different characteristics, namely a granular catalyst composed of a supported catalyst with a particle size greater than 0.65 mm and a slurry catalyst with an average particle size less than 300 μm, wherein the slurry catalyst can be prepared from a water-soluble metal precursor or from catalyst fine particles.

[0005] The literature (Fuel Processing Technology, 185, 2019, 158-168) reported the catalytic hydrocracking of HVGO using a Ni-TBC dispersed catalyst and a Ni-W / (SiO2-Al2O3 and Y-zeolite) supported catalyst, demonstrating the synergistic effect between dispersed and supported catalysts.

[0006] However, the hydrogenation activity of existing catalysts when used in hydroprocessing still needs to be improved. Summary of the invention

[0007] The purpose of the present invention is to provide a composite catalyst and a preparation method and application thereof, so as to solve the problem that the hydrogenation activity of the existing catalyst needs to be further improved when used for hydrogenation treatment.

[0008] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a composite catalyst, which includes a metal organic ligand catalyst and a molecular sieve catalyst; the metal organic ligand catalyst includes an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is one or more of VB group metals, VIB group metals, VIII group metals, IB group metals and IIB group metals; the organic ligand includes a hydrocarbon group and a coordination group; the molecular sieve catalyst includes a molecular sieve active component; the molecular sieve active component is one or more of A-type molecular sieve, X-type molecular sieve, Y-type molecular sieve and ZSM-5 molecular sieve.

[0009] Optionally, based on the dry weight of the metal organic ligand catalyst, the content of the active metal in the metal organic ligand catalyst is 2-50% by weight, preferably 10-30% by weight; based on the dry weight of the molecular sieve catalyst, the content of the molecular sieve active component in the molecular sieve catalyst is 10-50% by weight; the molar ratio between the active metal in the metal organic ligand catalyst and the organic ligand is 1:(0.5-3.5), preferably 1:(1.5-3); the mass ratio of the active metal in the metal organic ligand catalyst to the molecular sieve catalyst is 1:(1-10).

[0010] Optionally, the general formula of the metal organic ligand catalyst is: MO a[R(COOH) x ] b , wherein M represents the active metal, R(COOH) x Represents the organic ligand, R represents the hydrocarbon group in the organic ligand, COOH represents the coordinating group in the organic ligand, x represents the total number of the organic ligands, a represents the molar ratio of the non-coordinating bonded oxygen atoms connected to the active metal M to the active metal M, and b represents the molar ratio of the organic ligand to the active metal M, wherein: R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group and a C6-C12 aromatic group; x is 1, 2 or 3, preferably 1 or 2; a is a positive number of 0-5, preferably a positive number of 1-3; b is a positive number of 0.5-3.5, preferably a positive number of 1.5-3.

[0011] Optionally, the molecular sieve catalyst may include a matrix and a binder, the matrix is ​​one or more of Al2O3, kaolin, amorphous silica-alumina and kaolin; the binder is one or more of silica-alumina sol, silica sol and alumina sol; based on the dry weight of the molecular sieve catalyst, the content of the matrix in the molecular sieve catalyst is 0 to 70 weight %; the content of the binder is 0 to 50 weight %.

[0012] Optionally, the VB group metal, VIB group metal, VIII group metal, IB group metal and IIB group metal are one or more of V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, more preferably one or more of Mo, Ni and Co; the organic ligand is a C4-C20 organic carboxylic acid and / or an anhydride of the C4-C20 organic carboxylic acid, and the organic carboxylic acid is one or more of C4-C20 normal or isomeric alkyl carboxylic acid, C6-C20 cycloalkane carboxylic acid containing a saturated carbon ring and C7-C20 aromatic carboxylic acid containing an aromatic ring, preferably one or more of C4-C12 normal or isomeric alkyl carboxylic acid, C6-C13 cycloalkane carboxylic acid containing a saturated carbon ring and C7-C13 aromatic carboxylic acid containing an aromatic ring.

[0013] The second aspect of the present invention provides a method for preparing the composite catalyst provided by the first aspect of the present invention, the method comprising: mixing a metal organic ligand catalyst and a molecular sieve catalyst; the mass ratio of the metal organic ligand catalyst to the molecular sieve catalyst is 1:(1-10) based on metal.

[0014] Optionally, the method further comprises: mixing an active metal precursor with an organic carboxylic acid for a coordination reaction to prepare the metal organic ligand catalyst; the molar ratio of the metal element in the active metal precursor to the organic carboxylic acid is 1:(0.5-3.5).

[0015] Optionally, the active metal precursor is one or more of a soluble molybdenum-containing compound, a nickel-containing compound and a cobalt-containing compound, preferably one or more of ammonium heptamolybdate, ammonium molybdate, molybdic acid, nickel hydroxide and cobalt nitrate; the organic carboxylic acid is one or more of a C4-C12 normal or isomeric alkyl carboxylic acid, a C6-C13 cycloalkane carboxylic acid containing a saturated carbon ring and a C7-C13 aromatic carboxylic acid containing an aromatic ring; the reaction temperature of the coordination reaction is 160-260°C, and the reaction time is 2-8h.

[0016] The third aspect of the present invention provides a hydrocracking method for oil products, which comprises: under hydrogenation reaction conditions, the oil product raw material is contacted and pre-mixed with the composite catalyst provided by the first aspect of the present invention, and then enters a slurry bed reactor to contact with hydrogen and carry out hydrocracking and upgrading reactions.

[0017] Optionally, the oil raw material includes one or more of crude oil, gasoline, diesel, wax oil, residual oil, asphalt, coal tar, catalytic cracking oil slurry and biomass oil; the conditions of the hydrocracking and upgrading reaction include: based on the weight of the oil raw material, the amount of the metal organic ligand catalyst in the composite catalyst is 50-10000 μg / g, preferably 50-3000 μg / g; the amount of the molecular sieve catalyst is 50-100000 μg / g, preferably 50-30000 μg / g; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 300-500°C, preferably 350-450°C; the liquid hourly space velocity is 0.05-5.0h -1 , preferably 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

[0018] Through the above technical scheme, the composite catalyst of the present invention has a high hydrogenation activity. When used for oil hydrogenation, the coordination group of the organic ligand in the metal organic ligand catalyst forms a coordination bond with the active metal central atom or central ion through the oxygen atom, and it can be efficiently dispersed in the oil phase. During the reaction, it has a high hydrogenation activity; at the same time, a molecular sieve catalyst with an acidic function is added to promote the generation of carbon cations, effectively improve the cracking reaction of the oil, reduce the hydrogen consumption of the reaction system, and ensure that the product has a lower sulfur and nitrogen content.

[0019] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0021] Figure 1 is the infrared absorbance spectrum of the metal organic ligand catalyst prepared in Examples 1-3 of the present invention;

[0022] Figure 2 It is the infrared spectrum of pyridine of the molecular sieve catalyst of the present invention at different temperatures. DETAILED DESCRIPTION

[0023] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0024] The first aspect of the present invention provides a composite catalyst, which includes a metal organic ligand catalyst and a molecular sieve catalyst; the metal organic ligand catalyst includes an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is one or more of VB group metals, VIB group metals, VIII group metals, IB group metals and IIB group metals; the organic ligand includes a hydrocarbon group and a coordination group; the molecular sieve catalyst includes a molecular sieve active component, and the molecular sieve active component is one or more of A-type molecular sieve, X-type molecular sieve, Y-type molecular sieve and ZSM-5 molecular sieve.

[0025] The inventors of the present invention have found that the existing catalysts are usually oil-soluble precursors that are converted into sulfurized active phases in situ in the reaction system. XRD analysis shows that they are mainly amorphous C loads, so the catalysts do not have acidic functions. However, in the hydrofining and cracking reaction processes, it is necessary to increase the acidity of the catalyst to promote the hydrogenolysis reaction. Therefore, the present invention uses a composite catalyst with high hydrogenation activity, uses a molecular sieve catalyst to provide an acidic function, and the active metal in the metal organic ligand catalyst provides a hydrogenation function to promote hydrocracking and desulfurization, denitrogenation and other hydrofining reactions of oil products.

[0026] According to the present invention, optionally, based on the dry weight of the metal organic ligand catalyst, the content of the active metal in the metal organic ligand catalyst is 2-50% by weight, preferably 10-30% by weight; based on the dry weight of the molecular sieve catalyst, the content of the molecular sieve active component in the molecular sieve catalyst is 10-50% by weight.

[0027] According to the present invention, optionally, the molar ratio between the active metal in the metal organic ligand catalyst and the organic ligand is 1:(0.5-3.5), preferably 1:(1.5-3); the mass ratio between the active metal in the metal organic ligand catalyst and the molecular sieve catalyst is 1:(1-10), preferably 1:(1-5).

[0028] According to the present invention, optionally, the infrared spectrum of the metal organic ligand catalyst is in the range of 700-1000 cm -1 1350-1450cm -1 and 1500-1610cm -1 There is a characteristic peak at the position.

[0029] According to the present invention, optionally, the general formula of the metal organic ligand catalyst is: MO a [R(COOH) x ] b , wherein M represents the active metal, R(COOH) x Represents the organic ligand, R represents the hydrocarbon group in the organic ligand, COOH represents the coordinating group in the organic ligand, x represents the total number of the organic ligands, a represents the molar ratio of the non-coordinating bonded oxygen atoms connected to the active metal M to the active metal M, and b represents the molar ratio of the organic ligand to the active metal M, wherein: R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group and a C6-C12 aromatic group; x is 1, 2 or 3, preferably 1 or 2; a is a positive number of 0-5, preferably a positive number of 1-3; b is a positive number of 0.5-3.5, preferably a positive number of 1.5-3.

[0030] In the present invention, "C3-C19 hydrocarbon group" refers to a hydrocarbon group having 3-19 carbon atoms, which may be a saturated or unsaturated straight chain, branched chain or carbon ring hydrocarbon group, including but not limited to C3-C19 normal alkyl, C3-C19 isomeric alkyl, C5-C19 cycloalkyl and C6-C19 aromatic group.

[0031] In the present invention, "C5-C11 normal alkyl" refers to a straight-chain alkyl group having 5 to 11 carbon atoms, such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-undecyl.

[0032] In the present invention, "C5-C11 isomeric alkyl" refers to a branched alkyl group having 5 to 11 carbon atoms, such as isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl.

[0033] In the present invention, "C5-C12 cycloalkyl group" refers to a saturated hydrocarbon group containing a saturated carbocyclic ring having 5-12 carbon atoms, such as cyclopentyl, cyclohexyl, methylcyclohexyl, decahydronaphthyl, methyldecahydronaphthyl, ethyldecahydronaphthyl and the like.

[0034] In the present invention, "C6-C12 aryl group" refers to a group containing an aromatic ring having 6 to 12 carbon atoms, such as phenyl, naphthyl, anthracenyl, p-tolyl, benzyl, methylnaphthyl and the like.

[0035] In the present invention, the C3-C19 hydrocarbon group, C5-C11 normal alkyl group, C5-C11 isomeric alkyl group, C5-C12 cycloalkyl group and C6-C12 aryl group may be optionally substituted, for example, may be unsubstituted, or may be substituted by one or more groups selected from halogen, nitro, sulfonic acid group and the like.

[0036] According to the present invention, optionally, the molecular sieve catalyst optionally includes a matrix and a binder; the matrix is ​​one or more of Al2O3, kaolin, amorphous silica-alumina and white clay; the binder is one or more of silica-alumina sol, silica sol and alumina sol, and a variety of rare earth metal oxides are added, such as cerium oxide, lanthanum oxide, etc. Based on the dry weight of the molecular sieve catalyst, the content of the matrix in the molecular sieve catalyst is 0 to 70% by weight; the content of the binder is 0 to 50% by weight.

[0037] According to the present invention, optionally, the VB group metal, VIB group metal, VIII group metal, IB group metal and IIB group metal are one or more of V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, and more preferably one or more of Mo, Ni and Co.

[0038] According to the present invention, optionally, the organic ligand is an organic carboxylic acid of C4-C20 and / or an anhydride of the organic carboxylic acid of C4-C20, and the organic carboxylic acid is one or more of normal or isomeric alkyl carboxylic acids of C4-C20, cycloalkane carboxylic acids containing saturated carbon rings of C6-C20, and aromatic carboxylic acids containing aromatic rings of C7-C20, preferably one or more of normal or isomeric alkyl carboxylic acids of C4-C12, cycloalkane carboxylic acids containing saturated carbon rings of C6-C13, and aromatic carboxylic acids containing aromatic rings of C7-C13.

[0039] In the present invention, C4-C20 organic carboxylic acid refers to a monocarboxylic acid having 4-20 carbon atoms, and the organic carboxylic acid may be a saturated or unsaturated straight chain, branched chain or monocarboxylic acid having a carbon ring, including but not limited to C4-C20 normal alkyl carboxylic acids, C4-C20 isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbon rings, and C7-C20 aromatic carboxylic acids containing aromatic rings.

[0040] In the present invention, the organic carboxylic acid is further preferably one or more of succinic acid, caproic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, petroleum acid, salicylic acid, benzoic acid and phenylacetic acid.

[0041] The second aspect of the present invention provides a method for preparing the composite catalyst provided by the first aspect of the present invention, the method comprising: mixing a metal organic ligand catalyst and a molecular sieve catalyst; the mass ratio of the metal organic ligand catalyst to the molecular sieve catalyst is 1:(1-10) based on metal.

[0042] According to the present invention, optionally, the method further comprises: mixing an active metal precursor with an organic carboxylic acid for a coordination reaction to prepare the metal organic ligand catalyst; the molar ratio of the metal element in the active metal precursor to the organic carboxylic acid is 1:(0.5-3.5).

[0043] According to the present invention, optionally, the active metal precursor is one or more of a soluble molybdenum-containing compound, a nickel-containing compound and a cobalt-containing compound, preferably one or more of ammonium heptamolybdate, ammonium molybdate, molybdic acid, nickel hydroxide and cobalt nitrate; the metal organic ligand catalyst obtained by the active metal precursor is a catalyst used for oil hydrogenation, which can be highly dispersed in the oil phase, such as an oil-soluble molybdenum catalyst, an oil-soluble molybdenum-cobalt catalyst, an oil-soluble molybdenum-nickel catalyst, etc.

[0044] According to the present invention, optionally, the organic carboxylic acid is one or more of a C4-C12 normal or isomeric alkyl carboxylic acid, a C6-C13 cycloalkane carboxylic acid containing a saturated carbon ring, and a C7-C13 aromatic carboxylic acid containing an aromatic ring.

[0045] According to the present invention, optionally, the reaction temperature of the coordination reaction is 150-350° C., and the reaction time is 2-8 h.

[0046] The third aspect of the present invention provides a hydrocracking method for oil products, which comprises: under hydrogenation reaction conditions, the oil product raw material is contacted with the composite catalyst provided by the first aspect of the present invention for premixing, and then entering a slurry bed reactor to contact with hydrogen and perform hydrocracking and upgrading reactions to obtain a hydrogenated product.

[0047] According to the present invention, optionally, tailings containing catalyst are separated from the hydrogenation product and returned to the reaction system for catalytic conversion, wherein part of the tailings is discharged from the reaction system to ensure catalyst activity and maintain long-term operation.

[0048] In the present invention, the metal organic ligand catalyst in the composite catalyst can be highly dispersed in the oil product, dissociate hydrogen to produce hydrogen free radicals, which not only effectively reduces the coke yield, but also can seal hydrocarbon free radicals to produce small molecule oil and gas products; at the same time, a molecular sieve catalyst with acidic function is added to promote the generation of carbon cations, effectively improve the cracking reaction of the oil product, and reduce the hydrogen consumption of the reaction system, which can ensure that the product has a lower sulfur and nitrogen content.

[0049] According to the present invention, optionally, the oil raw material includes one or more of crude oil, gasoline, diesel, wax oil, residual oil, asphalt, coal tar, catalytic cracking slurry and biomass oil.

[0050] According to the present invention, optionally, the conditions of the hydrocracking and upgrading reactions include: based on the weight of the oil product raw material, the amount of the metal organic ligand catalyst in the catalyst system is 50-10000 μg / g, preferably 50-300 μg / g; the amount of the molecular sieve catalyst is 50-100000 μg / g, preferably 50-30000 μg / g; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 300-500°C, preferably 350-450°C; the liquid hourly space velocity is 0.05-5.0h -1 , preferably 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

[0051] The present invention is further illustrated by the following examples, but the present invention is not limited thereto.

[0052] Unless otherwise specified, the raw materials used in the examples can be obtained through commercial sources.

[0053] Examples 1-3

[0054] Examples 1-3 are the preparation of composite catalysts C1-C3.

[0055] The preparation method of the metal organic ligand catalyst used in Examples 1-3 includes: adding an active metal precursor compound into a three-necked flask, and then adding an organic carboxylic acid to mix and react to obtain a metal organic acid complex product, namely, a metal organic ligand catalyst. The metal content and infrared spectrum of the obtained product are measured, and the composition of the obtained product is determined based on the measured results.

[0056] The preparation method of the composite catalysts C1-C3 in Examples 1-3 includes: mixing a metal organic ligand catalyst and a molecular sieve catalyst (Y-type molecular sieve).

[0057] The raw materials, reaction conditions, product compositions, etc. in Examples 1-3 are shown in Table 1.

[0058] Table 1

[0059]

[0060]

[0061] Examples 4-5 and Comparative Examples 1-2

[0062] Examples 4-5 and Comparative Examples 1-2 use oil feedstock A to evaluate the performance of the composite catalyst.

[0063] Raw material A is catalytic cracking oil slurry with a distillation range of 162-645° C., a sulfur mass fraction of 1.07%, a nitrogen mass fraction of 0.14%, and a tricyclic + tetracyclic aromatic hydrocarbon mass fraction of 47.6%.

[0064] In Example 4 and Example 5, the composite catalyst prepared in Example 3 is used to directly treat the raw material A. Specifically, under the conditions of hydrogenation reaction, 200g of raw material A is contacted with the composite catalyst for premixing, and then enters into a 2L intermittent high-pressure reactor to contact with hydrogen and perform hydrocracking and upgrading reactions to obtain hydrogenated products. In Comparative Examples 1 and 2, the metal organic ligand catalyst and molecular sieve catalyst prepared in Example 3 are used to treat raw material A respectively. The reaction conditions are shown in Table 2. The hydrogenated product obtained by the reaction is distilled and cut, and a VGO fraction oil of 350-500°C is selected. The operating pressure is 10mmHg at 350°C and 0.3mmHg at 500°C. The VGO fraction oil is analyzed for S content and hydrocarbon composition, and the experimental results are shown in Table 2.

[0065] Table 2

[0066]

[0067] Examples 6-7 and Comparative Examples 3-4

[0068] Examples 6-7 and Comparative Examples 3-4 use oil feedstock B to evaluate the catalyst performance.

[0069] Raw material B is vacuum residue oil, with a sulfur mass fraction of 6.4%, a nitrogen mass fraction of 0.57%, an asphaltene mass fraction of 14%, a residual carbon value of 26.4%, and a heavy metal (Ni+V) ratio of 210 μg / g.

[0070] In Example 6, the composite catalyst prepared in Example 1 was used to directly treat the raw material B, and in Example 7, the composite catalyst prepared in Example 2 was used to directly treat the raw material B. Specifically, under the conditions of hydrogenation reaction, 200g of raw material B was contacted with the composite catalyst for premixing, and then contacted with hydrogen in a 2L intermittent high-pressure reactor for hydrocracking and upgrading reaction to obtain a hydrogenated product. Comparative Examples 3 and 4 were respectively used to treat the raw material B using the metal organic ligand catalysts prepared in Example 1 and Example 2. The reaction conditions and experimental results are shown in Table 3.

[0071] Table 3

[0072] project Example 6 Example 7 Comparative Example 3 Comparative Example 4 catalyst Composite Catalyst C1 Composite Catalyst C2 Metal-organic ligand catalysts Metal-organic ligand catalysts Reaction temperature / ℃ 425 425 425 425 Reaction time / min 130 130 130 130 Hydrogen initial pressure / MPa 9 9 9 9 Residue oil cracking rate / % 66.45 67.85 65.91 84.72 Condensation rate / % 0.67 0.58 0.72 3.87 Desulfurization rate / % 81.29 85.26 77.32 84.14 Denitrification rate / % 52.61 52.26 50.58 51.55 Hydrogen consumption 2.12 2.00 2.49 2.88

[0073] Test Case

[0074] Test Example 1

[0075] Method for determining the metal content in the metal organic acid complex of the metal organic ligand catalyst obtained in Examples 1-3: After the test sample is diluted 200 times with an organic solvent, it is determined using a SPECTRO ARCOS SOP plasma emission spectrometer using inductively coupled plasma optical emission spectrometry (ICP-OES). The measurement conditions are a closed optical chamber filled with argon, vertical observation, and a wavelength range of 130nm-770nm.

[0076] Test Example 2

[0077] Example 1-3 Infrared spectrum measurement method of the metal organic ligand catalyst obtained: The infrared spectrum of the solid catalyst product obtained was measured using a NICOLET IS50 spectrometer from Thermo Fisher, under the scanning wavelength of 400-4000 cm -1 The number of scans is 16. ZnSe crystal and HgCdTe infrared detector are used together to measure the attenuated total reflectance (ATR) of the sample with a resolution of 4cm -1 .

[0078] The infrared absorbance spectra of the metal organic ligand catalysts prepared in Examples 1-3 are as follows: Figure 1 As shown in the figure, it can be clearly seen that the metal organic ligand catalysts are all in the range of 700-1000cm -1 1350-1450cm -1 and 1500-1610cm -1 There is a characteristic peak at the position. 700-1000cm -1 There are MO and M=O vibration characteristic peaks at 1350-1450cm -1 and 1500-1610cm -1There is a characteristic peak at the position of -C(=O)-O group coordinated with the metal.

[0079] Test Example 3

[0080] The molecular sieve catalyst was analyzed by XRF using Rigaku 3013 produced by Rigaku Company, and the element mass fractions of the molecular sieve catalyst were obtained as shown in Table 4. As shown in Table 4, the molecular sieve catalyst is mainly composed of silicon aluminum oxide, which accounts for more than 90%, and is doped with a small amount of oxides of elements such as cerium, phosphorus, lanthanum, and iron. The deposited coke content is also low, indicating that it is burned more thoroughly.

[0081] Table 4

[0082]

[0083]

[0084] Test Example 4

[0085] The acidity of the molecular sieve catalyst was analyzed using the FTS3000 Fourier transform infrared spectrometer produced by BIO-RAD, USA, under the action of pyridine probe. The results are as follows: Figure 2 As shown. Pyridine molecules can be The acid center forms a PyH+ species and forms a Py-L coordination complex with Lewis acid at 1540 cm -1 and 1450cm -1 The characteristic absorption peak is generated at the position of the pyridine molecule, and the desorption temperature of the pyridine molecule is proportional to the acid strength. Generally, the acid amount at 250°C is taken as the total acid amount, and the acid amount at 350°C is taken as the medium-strong acid amount. The peak area is integrated and the acid amount is calculated. The total acid amount of B acid is 2.7μmol / g, the total acid amount of L acid is 11.0μmol / g, the medium-strong acid amount of B acid is 1.1μmol / g, and the medium-strong acid amount of L acid is 5.0μmol / g. From the data, it can be seen that the molecular sieve catalyst is mainly Lewis acid, and more than 40% is medium-strong acid, which is strong in acidity.

[0086] As can be seen from the results of Table 2, under the same reaction conditions, compared with the metal organic ligand catalyst of Comparative Example 1 and the molecular sieve catalyst of Comparative Example 2 alone, under the action of the composite catalyst of Example 3, the S and N contents in the product are lower, the contents of three-ring and four-ring aromatic hydrocarbons are increased, and the hydrogen consumption is also reduced. As can be seen from the results of Table 3, compared with the metal organic ligand catalyst of Comparative Example 3 and Comparative Example 4 alone, under the same reaction conditions, the composite catalysts of Examples 1 and 2 of the present invention have higher hydrogenation activity, higher residual oil cracking rate, lower condensation rate and higher desulfurization and denitrification rates, and the hydrogen consumption is significantly reduced.

[0087] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0088] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0089] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A composite catalyst, characterized in that: The composite catalyst comprises a metal organic ligand catalyst and a molecular sieve catalyst; The metal organic ligand catalyst comprises an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is one or more of VB group metals, VIB group metals, VIII group metals, IB group metals and IIB group metals; the organic ligand comprises a hydrocarbon group and a coordination group; The molecular sieve catalyst comprises a molecular sieve active component; the molecular sieve active component is one or more of A-type molecular sieve, X-type molecular sieve, Y-type molecular sieve and ZSM-5 molecular sieve.

2. The composite catalyst according to claim 1, wherein Based on the dry weight of the metal organic ligand catalyst, the active metal content in the metal organic ligand catalyst is 2-50% by weight, preferably 10-30% by weight; Based on the dry weight of the molecular sieve catalyst, the content of the molecular sieve active component in the molecular sieve catalyst is 10 to 50 weight %; The molar ratio between the active metal and the organic ligand in the metal organic ligand catalyst is 1:(0.5-3.5), preferably 1:(1.5-3); The mass ratio of the active metal in the metal organic ligand catalyst to the molecular sieve catalyst is 1:(1-10).

3. The composite catalyst according to claim 1, wherein The general formula of the metal organic ligand catalyst is: MO a [R(COOH) x ] b , Wherein, M represents the active metal, R(COOH) x represents the organic ligand, R represents the hydrocarbon group in the organic ligand, COOH represents the coordinating group in the organic ligand, x represents the total number of the organic ligands, a represents the molar ratio of the non-coordinating oxygen atoms connected to the active metal M to the active metal M, and b represents the molar ratio of the organic ligand to the active metal M, wherein: R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group, and a C6-C12 aryl group; x is 1, 2 or 3, preferably 1 or 2; a is a positive number between 0 and 5, preferably a positive number between 1 and 3; b is a positive number of 0.5-3.5, preferably a positive number of 1.5-3.

4. The composite catalyst according to claim 1, wherein The molecular sieve catalyst may optionally include a matrix and a binder; the matrix is ​​one or more of Al2O3, kaolin, amorphous aluminum silicate and clay; the binder is one or more of silica-alumina sol, silica sol and aluminum sol; Based on the dry weight of the molecular sieve catalyst, the content of the matrix in the molecular sieve catalyst is 0 to 70 weight %; the content of the binder is 0 to 50 weight %.

5. The composite catalyst according to claim 1, wherein The VB group metal, VIB group metal, VIII group metal, IB group metal and IIB group metal are one or more of V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, more preferably one or more of Mo, Ni and Co; The organic ligand is an organic carboxylic acid of C4-C20 and / or an anhydride of the organic carboxylic acid of C4-C20, and the organic carboxylic acid is one or more of normal or isomeric alkyl carboxylic acids of C4-C20, cycloalkane carboxylic acids containing saturated carbon rings of C6-C20, and aromatic carboxylic acids containing aromatic rings of C7-C20, preferably one or more of normal or isomeric alkyl carboxylic acids of C4-C12, cycloalkane carboxylic acids containing saturated carbon rings of C6-C13, and aromatic carboxylic acids containing aromatic rings of C7-C13.

6. A method for preparing the composite catalyst according to any one of claims 1 to 5, characterized in that: The method comprises: mixing a metal organic ligand catalyst and a molecular sieve catalyst; Calculated on the basis of metal, the mass ratio of the metal organic ligand catalyst to the molecular sieve catalyst is 1:(1-10).

7. The method according to claim 6, wherein: The method further comprises: mixing an active metal precursor with an organic carboxylic acid to carry out a coordination reaction to prepare the metal organic ligand catalyst; The molar ratio of the metal element to the organic carboxylic acid in the active metal precursor is 1:(0.5-3.5).

8. The method according to claim 7, wherein: The active metal precursor is one or more of a soluble molybdenum-containing compound, a nickel-containing compound and a cobalt-containing compound, preferably one or more of ammonium heptamolybdate, ammonium molybdate, molybdic acid, nickel hydroxide and cobalt nitrate; The organic carboxylic acid is one or more of a C4-C12 normal or isomeric alkyl carboxylic acid, a C6-C13 cycloalkane carboxylic acid containing a saturated carbon ring, and a C7-C13 aromatic carboxylic acid containing an aromatic ring; The reaction temperature of the complexing reaction is 150-350° C., and the reaction time is 2-8 hours.

9. A hydrocracking method for oil products, characterized in that: The method includes: Under the conditions of hydrogenation reaction, the oil raw material is contacted with the composite catalyst described in any one of claims 1 to 5 for premixing, and then enters into a slurry bed reactor for contact with hydrogen and undergoes hydrocracking and upgrading reactions.

10. The method according to claim 9, wherein: The oil raw material includes one or more of crude oil, gasoline, diesel, wax oil, residual oil, asphalt, coal tar, catalytic cracking slurry and biomass oil; The conditions of the hydrocracking and upgrading reaction include: based on the weight of the oil product raw material, the amount of the metal organic ligand catalyst in the composite catalyst is 50-10000 μg / g, preferably 50-3000 μg / g; the amount of the molecular sieve catalyst is 50-100000 μg / g, preferably 50-30000 μg / g; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 300-500°C, preferably 350-450°C; the liquid hourly space velocity is 0.05-5.0h -1 , preferably 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

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