Composite catalyst, its preparation method and application

Abstract

The present application relates to a kind of composite catalyst and its preparation method and application, the composite catalyst includes metal organic ligand catalyst and molecular sieve catalyst;The metal organic ligand catalyst includes active metal center atom or center ion and the organic ligand of coordination with the active metal center atom or center ion;The active metal is one or more in VB group metal, VIB group metal, VIII group metal, IB group metal and ⅡB group metal;The organic ligand includes hydrocarbon group and coordination group;The molecular sieve catalyst includes molecular sieve active component.The composite catalyst of the present application has higher hydrogenation activity, when being used for oil product hydrogenation, metal organic ligand catalyst provides hydrogenation function, molecular sieve catalyst provides acidic function, promotes carbenium ion generation, effectively improves oil product cracking reaction, reduces the hydrogen consumption of reaction system, can ensure that product has lower sulfur, nitrogen content.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, in particular to a composite catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydrofining of petroleum products, including hydrodesulfurization, denitrification, and demetallization, has always been an important part of the field of petroleum chemical industry. With increasingly stringent environmental regulations and rapid economic development, there is a rapid increase in demand for light oil and gas and chemical raw materials, and it is increasingly important to develop catalysts for efficient processing of heavy feedstocks. Traditional hydrofining catalysts are fixed-bed supported catalysts, which are usually composed of active metals and supports. The active metals usually have hydrogenation activity, and the supports are alumina or mixtures thereof with other oxides (such as ZrO2, MgO, etc.), which can provide the required acidity for cracking reactions. Supported catalysts have become the most widely used catalysts in industrial applications due to their high catalytic activity, strong mechanical strength, and mature process technology. However, with the increasing quality of crude oil, environmental protection and downstream devices require more stringent requirements for oil products. Supported catalysts need to be upgraded and replaced due to their low diffusion mass transfer efficiency and easy coking and deactivation. The dispersed catalysts used in slurry bed processing have the characteristics of oil solubility, nanoscale size, and high hydrogenation activity, which can overcome steric hindrance, efficiently convert heavy components, and avoid the problem of short operation cycle caused by coking and fouling. At the same time, due to the characteristics of pseudo-homogeneous phase and high mass and heat transfer efficiency of the slurry bed processing system, it has high tolerance to solid content, small temperature difference in the reactor, and can be operated at high temperature, so it is considered as an effective way to hydrogenate and modify heavy oil products, especially poor quality raw materials. However, since the slurry bed catalyst is generally converted from a precursor in situ to an active phase with sulfide characteristics, it usually does not have acidic function, so in the slurry bed hydrogenation system, it is generally dominated by hydrothermal cracking. Unlike the carbonium ion mechanism of catalytic cracking, thermal cracking is usually composed of initiation, propagation, and termination steps of free radicals, and has the characteristics of high required temperature, low activity, and randomness, so many researchers use a combination of two catalysts to process petroleum products.

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

[0004] CN103228355A discloses a dual catalyst system applied in a boiling bed reactor, including two different catalysts with different characteristics, namely a particle catalyst with particle size greater than 0.65 mm composed of a supported catalyst and a slurry catalyst with 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 document (Fuel Processing Technology, 185, 2019, 158-168) reports the co-catalysis of Ni-TBC dispersion catalyst and Ni-W / (SiO2-Al2O3 and Y-zeolite) supported catalyst for hydrocracking HVGO, proving the synergy between dispersion and supported catalysts.

[0006] However, the existing catalysts still need to be improved in hydrogenation activity when used for hydroprocessing. SUMMARY

[0007] The purpose of the present application is to provide a composite catalyst and its preparation method and application, in order to solve the problem that the existing catalysts need to be further improved in hydrogenation activity when used for hydroprocessing.

[0008] To achieve the above purpose, the first aspect of the present application provides a composite catalyst, which comprises a metal organic ligand catalyst and a molecular sieve catalyst; the metal organic ligand catalyst comprises an active metal center atom or center ion and an organic ligand coordinated with the active metal center atom or center 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 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.

[0009] Optionally, the content of the active metal in the metal organic ligand catalyst is 2-50 wt%, preferably 10-30 wt%, based on the dry basis weight of the metal organic ligand catalyst; the content of the molecular sieve active component in the molecular sieve catalyst is 10-50 wt%, based on the dry basis weight of the molecular sieve catalyst; 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).

[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 radical in the organic ligand, COOH represents the coordinating group in the organic ligand, x represents the total number of the organic ligand, a represents the molar ratio of the non-coordinating oxygen atom linked 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 radical, preferably a C5-C11 n- or iso-alkyl radical, a C5-C12 cycloalkyl radical containing a saturated carbon ring, and a C6-C12 aryl radical; x is 1, 2 or 3, preferably 1 or 2; a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and b is a positive number from 0.5 to 3.5, preferably a positive number from 1.5 to 3.

[0011] Optionally, the molecular sieve catalyst comprises 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; the content of the matrix in the molecular sieve catalyst is 0-70% by weight based on the dry base weight of the molecular sieve catalyst; the content of the binder is 0-50% by weight.

[0012] Optionally, the group VB metal, group VIB metal, group VIII metal, group IB metal and group II B metal is 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, the organic carboxylic acid is one or more of a C4-C20 n- or iso-alkyl carboxylic acid, a C6-C20 cycloalkyl carboxylic acid containing a saturated carbon ring and a C7-C20 aromatic carboxylic acid containing an aromatic ring, preferably one or more of a C4-C12 n- or iso-alkyl carboxylic acid, a C6-C13 cycloalkyl carboxylic acid containing a saturated carbon ring and a C7-C13 aromatic carboxylic acid containing an aromatic ring.

[0013] The second aspect of the present application provides a method for preparing the composite catalyst provided by the first aspect of the present application, 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) on a metal basis.

[0014] Optionally, the method further comprises: mixing the active metal precursor with an organic carboxylic acid to perform a complexation reaction to prepare the metal-organic ligand catalyst; and 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 soluble molybdenum-containing compounds, nickel-containing compounds and cobalt-containing compounds, and 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 C4-C12 normal or isoalkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing saturated carbon rings and C7-C13 aromatic carboxylic acids containing aromatic rings; and the complexation reaction is performed at a reaction temperature of 160-260℃ for 2-8h.

[0016] The third aspect of the present application provides a hydrocracking method for oil products, which comprises: contacting an oil product raw material with the composite catalyst provided by the first aspect of the present application under the conditions of a hydrogenation reaction, and then entering a slurry bed reactor to contact hydrogen and perform a hydrocracking and upgrading reaction.

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

[0018] By the above technical solution, the composite catalyst of the present application has high hydrogenation activity; when used for oil product hydrogenation, the coordination groups of the organic ligand in the metal-organic ligand catalyst form coordination bonds with the active metal center atom or center ion through oxygen atoms, which can be highly dispersed in the oil phase and has high hydrogenation activity in the reaction process; and the addition of the molecular sieve catalyst with acidic function promotes the generation of carbonium ions, effectively improves the cracking reaction of the oil product, reduces the hydrogen consumption of the reaction system, and can ensure that the product has lower sulfur and nitrogen contents.

[0019] Other features and advantages of the present application will be illustrated in the following detailed description of the embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:

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

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

[0023] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0024] The first aspect of the present application provides a composite catalyst, which comprises a metal organic ligand catalyst and a molecular sieve catalyst; the metal organic ligand catalyst comprises an active metal center atom or ion and an organic ligand coordinated with the active metal center atom or 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 a hydrocarbon group and a coordination group; the molecular sieve catalyst comprises a molecular sieve active component, which 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 application found that the existing catalysts are generally oil-soluble precursors which are converted into sulfidized active phase in situ in the reaction system, and the XRD analysis shows that they are mainly amorphous C supported, so the catalysts do not have acid function. However, in the process of hydrofining and cracking, the acid of the catalyst needs to be improved to promote the hydrogenolysis reaction, so the present application adopts a composite catalyst with high hydrogenation activity, which utilizes the acid function provided by the molecular sieve catalyst and the hydrogenation function provided by the active metal in the metal organic ligand catalyst to promote the hydrocracking and desulfurization, denitrification and other hydrofining reactions of oil products.

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

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

[0028] According to the present invention, optionally, the infrared spectrum of the organometallic ligand catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0029] According to the present invention, optionally, the general formula of the metal-organic ligand catalyst is: MO a [R(COOH) x ] b Where M represents the active metal, and R(COOH) x The organic ligand is represented by R, which represents the hydrocarbon group in the organic ligand, COOH represents the coordinating group in the organic ligand, x represents the total number of organic ligands, a represents the molar ratio of non-coordinated 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 isoalkyl 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 from 0 to 5, preferably a positive number from 1 to 3; and b is a positive number from 0.5 to 3.5, preferably a positive number from 1.5 to 3.

[0030] In this invention, "C3-C19 hydrocarbon group" refers to a hydrocarbon group having 3-19 carbon atoms. The hydrocarbon group can be a saturated or unsaturated straight-chain, branched, or carbon ring hydrocarbon group, including but not limited to C3-C19 normal alkyl, C3-C19 isoalkyl, C5-C19 cycloalkyl, and C6-C19 aryl.

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

[0032] In this invention, "C5-C11 isoalkyl" refers to branched alkyl groups having 5-11 carbon atoms, such as isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl.

[0033] In the present application, "C5-C12 cycloalkyl-containing" refers to a saturated hydrocarbon group containing a saturated carbon ring having 5-12 carbon atoms, such as cyclopentyl, cyclohexyl, methylcyclohexyl, decalinyl, methyldecalinyl, ethyldecalinyl, and the like.

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

[0035] In the present application, the C3-C19 hydrocarbon group, C5-C11 n-alkyl group, C5-C11 isoalkyl group, C5-C12 cycloalkyl-containing group, and C6-C12 aryl group can be optionally substituted, such as unsubstituted, or can be substituted with one or more groups selected from halogen, nitro, sulfonic acid group, and the like.

[0036] According to the present application, optionally, the molecular sieve catalyst can comprise 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 sol, alumina sol, and silica-alumina sol, and further adding one or more rare earth metal oxides, such as cerium oxide, lanthanum oxide, and the like. The content of the matrix in the molecular sieve catalyst is 0-70% by weight, and the content of the binder is 0-50% by weight, based on the dry weight of the molecular sieve catalyst.

[0037] According to the present application, optionally, the Group VB metal, Group VIB metal, Group VIII metal, Group IB metal, and Group ⅡB 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 application, optionally, the organic ligand is a C4-C20 organic carboxylic acid and / or an anhydride of the C4-C20 organic carboxylic acid, the organic carboxylic acid is one or more of a C4-C20 n- or isoalkyl carboxylic acid, a C6-C20 cycloalkyl carboxylic acid containing a saturated carbon ring, and a C7-C20 aromatic carboxylic acid containing an aromatic ring, preferably one or more of a C4-C12 n- or isoalkyl carboxylic acid, a C6-C13 cycloalkyl carboxylic acid containing a saturated carbon ring, and a C7-C13 aromatic carboxylic acid containing an aromatic ring.

[0039] In the present application, the C4-C20 organic carboxylic acid refers to a monovalent carboxylic acid with carbon atom number of 4-20, which can be a saturated or unsaturated straight chain, branched chain or monocyclic carboxylic acid with carbon ring, including but not limited to C4-C20 n-alkyl carboxylic acid, C4-C20 iso-alkyl carboxylic acid, C6-C20 cycloalkane carboxylic acid containing saturated carbon ring and C7-C20 aromatic carboxylic acid containing aromatic ring.

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

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

[0042] According to the present application, the method optionally further comprises: mixing an active metal precursor with an organic carboxylic acid to perform a complexation reaction to prepare the metal organic ligand catalyst; and 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 application, the active metal precursor is one or more of soluble molybdenum-containing compounds, nickel-containing compounds and cobalt-containing compounds, and is preferably one or more of ammonium heptamolybdate, ammonium molybdate, molybdic acid, nickel hydroxide and cobalt nitrate; and the metal organic ligand catalyst obtained by the active metal precursor is a catalyst for oil hydrogenation, which can be highly dispersed in oil phase, such as oil-soluble molybdenum catalyst, oil-soluble molybdenum-cobalt catalyst, oil-soluble molybdenum-nickel catalyst and the like.

[0044] According to the present application, the organic carboxylic acid is one or more of C4-C12 n-alkyl carboxylic acid, C6-C13 cycloalkane carboxylic acid containing saturated carbon ring and C7-C13 aromatic carboxylic acid containing aromatic ring.

[0045] According to the present application, the reaction temperature of the complexation reaction is 150-350℃, and the reaction time is 2-8h.

[0046] The third aspect of the present application provides a hydrocracking method for oil, which comprises: under the conditions of hydrocracking reaction, contacting an oil feedstock with the composite catalyst provided by the first aspect of the present application after pre-mixing, and then contacting with hydrogen in a slurry bed reactor to perform hydrocracking and upgrading reaction, thereby obtaining a hydrogenation product.

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

[0048] In the present application, the metal organic ligand catalyst in the composite catalyst can be highly dispersed in oil products, dissociate hydrogen to generate hydrogen radicals, effectively reduce the yield of coke, and close hydrocarbon radicals to generate small molecular oil gas products; meanwhile, the molecular sieve catalyst with acidic function is added to promote the generation of carbonium ions, effectively improve the cracking reaction of oil products, reduce hydrogen consumption of the reaction system, and ensure lower sulfur and nitrogen content in the products.

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

[0050] According to the present application, optionally, the conditions of the hydrogenation cracking and modification reaction include: the amount of the metal organic ligand catalyst in the catalyst system is 50-10000 μg / g, preferably 50-300 μg / g, based on the weight of the oil product raw material, in terms of metal; 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 ℃, preferably 350-450 ℃; the liquid hourly space velocity is 0.05-5.0 h -1 , preferably 0.05-1.0 h -1 ; and the hydrogen-oil volume ratio is 100-3000, preferably 200-2000.

[0051] The present application is further illustrated by the following examples, but the present application is not limited in any way by the examples.

[0052] The raw materials used in the examples can be obtained by commercial purchase, unless otherwise specified.

[0053] Examples 1-3

[0054] Examples 1-3 are the preparation of the composite catalyst 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 mixture for reaction to obtain a metal organic acid complex product, which is the metal organic ligand catalyst. The metal content and infrared spectrum of the obtained product are determined, and the composition of the obtained product is determined according to the measured results.

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

[0057] The raw materials, reaction conditions, product compositions 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 are to evaluate the performance of the composite catalysts by using oil raw material A.

[0063] The raw material A is catalytic cracking slurry oil, with a distillation range of 162-645℃, a sulfur mass fraction of 1.07%, a nitrogen mass fraction of 0.14%, and a mass fraction of tri- and tetra-cyclic aromatic hydrocarbons of 47.6%.

[0064] Examples 4 and 5 directly treat the raw material A by using the composite catalyst prepared in Example 3, specifically, 200g of the raw material A is pre-mixed with the composite catalyst, and then is put into a 2L volume batch high-pressure reactor to contact with hydrogen and to perform hydrocracking and upgrading reactions, to obtain a hydrogenation product. Comparative Examples 1 and 2 are to treat the raw material A by using the metal organic ligand catalyst and the molecular sieve catalyst prepared in Example 3 respectively. The reaction conditions are shown in Table 2. The hydrogenation product obtained by the reaction is subjected to distillation cutting, and the VGO fraction oil in the range of 350-500℃ is selected, and the operating pressure is 10mmHg at 350℃ and 0.3mmHg at 500℃, and the VGO fraction oil is subjected to S content and hydrocarbon composition analysis, 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 are to evaluate the performance of the catalysts by using oil raw material B.

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

[0070] Example 6 uses the composite catalyst prepared in Example 1 to directly treat the raw material B, and Example 7 uses the composite catalyst prepared in Example 2 to directly treat the raw material B. Specifically, 200 g of the raw material B is pre-mixed with the composite catalyst, and then is contacted with hydrogen in a 2 L batch autoclave under the conditions of a hydrogenation reaction to obtain a hydrogenation product. Comparative Examples 3 and 4 are to treat the raw material B with the metal-organic ligand catalysts prepared in Example 1 and Example 2, respectively. The reaction conditions and experimental results are shown in Table 3.

[0071] Table 3

[0072] Item Example 6 Example 7 Comparative Example 3 Comparative Example 4 Catalyst Composite catalyst C1 Composite catalyst C2 Metal organic ligand catalyst Metal organic ligand catalyst Reaction temperature / °C 425 425 425 425 Reaction time / min 130 130 130 130 Initial hydrogen pressure / MPa 9 9 9 9 Residue 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 Denitrogenation rate / % 52.61 52.26 50.58 51.55 Hydrogen consumption 2.12 2.00 2.49 2.88

[0073] Test Example

[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: The test sample is diluted 200 times with an organic solvent, and then is determined by inductively coupled plasma optical emission spectrometry (ICP-OES) using a SPECTRO ARCOS SOP plasma emission spectrometer under the following conditions: the light chamber is sealed with argon, vertical observation, and the wavelength range is 130 nm-770 nm.

[0076] Test Example 2

[0077] Method for determining the infrared spectrum of the metal-organic ligand catalyst obtained in Examples 1-3: The infrared spectrum of the obtained solid catalyst product is determined by a NICOLET IS50 spectrometer of Thermo Fisher Company under the following conditions: the scanning wavelength is 400-4000 cm -1 , and the scanning number is 16. The ZnSe crystal and mercury cadmium telluride infrared detector are used together to determine the attenuated total reflection ratio (ATR) of the sample, and the resolution is 4 cm -1 .

[0078] The infrared absorbance spectrum of the metal-organic ligand catalyst prepared in Examples 1-3 is shown in Figure 1 . As can be clearly seen from the figure, the metal-organic ligand catalyst has characteristic peaks at 700-1000 cm -1 , 1350-1450 cm -1 , and 1500-1610 cm -1 . The 700-1000 cm -1 position has M-O and M=O vibration characteristic peaks, the 1350-1450 cm -1 , and the 1500-1610 cm -1Characteristic peaks of -C(=O)-O group coordinating with metal at the position.

[0079] Test Example 3

[0080] The molecular sieve catalyst was subjected to XRF analysis by using a Rigaku 3013 produced by Rigaku Company, and the element mass fraction of the molecular sieve catalyst was obtained as shown in Table 4. As shown in Table 4, the molecular sieve catalyst mainly contains silicon aluminum oxide, and the proportion is more than 90%, wherein a small amount of oxide of cerium, phosphorus, lanthanum, iron and the like is doped, and the content of deposited coke is also low, indicating that the coke burning is more complete.

[0081] Table 4

[0082]

[0083]

[0084] Test Example 4

[0085] The acid analysis of the molecular sieve catalyst was carried out by using a FTS3000 Fourier transform infrared spectrometer produced by BIO-RAD Company of the United States under the action of a pyridine probe, and the results are shown in Table 5. Figure 2 Pyridine molecules can form PyH+ species with acid centers and form Py-L coordination complexes with Lewis acids, and characteristic absorption peaks are generated at 1540 cm -1 and 1450 cm -1 , respectively, and the temperature of pyridine molecule desorption is proportional to the acid strength. Generally, the acid amount under the condition of 250°C is taken as the total acid amount, and the acid amount under the condition of 350°C is taken as the medium-strong acid amount, the peak area is integrated and calculated to obtain the acid amount. The total B acid amount is 2.7 μmol / g, the total L acid amount is 11.0 μmol / g, the medium-strong B acid amount is 1.1 μmol / g, and the medium-strong L acid amount is 5.0 μmol / g. As shown by the data, the molecular sieve catalyst mainly contains Lewis acid, and more than 40% thereof is medium-strong acid, and the acidity is relatively strong.

[0086] As shown by the results in 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, the S and N contents in the product are lower, the content of tricyclic and tetracyclic aromatic hydrocarbons is increased, and the hydrogen consumption is also reduced under the action of the composite catalyst of Example 3. As shown by the results in Table 3, compared with the metal organic ligand catalyst of Comparative Example 3 and Comparative Example 4, under the same reaction conditions, the composite catalysts of Example 1 and Example 2 have higher hydrogenation activity, higher residue cracking rate, lower condensation rate, higher desulfurization and denitrification rate, and the hydrogen consumption is obviously reduced.

[0087] The preferred embodiments of the present application are described in detail above with reference to the drawings, but the present application is not limited to the specific details of the above-described embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0088] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, various possible combinations are not described again by the present application.

[0089] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should also be considered as disclosed by the present application.

Claims

1. A composite catalyst characterized in that, The composite catalyst comprises a metal organic ligand catalyst and a molecular sieve catalyst; the composite catalyst is prepared by mixing the metal organic ligand catalyst and the molecular sieve catalyst; The metal organic ligand catalyst comprises an active metal center atom or ion and an organic ligand coordinated with the active metal center atom or 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 VB group metal, VIB group metal, VIII group metal, IB group metal and ⅡB group metal is one or more of V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn; 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; The mass ratio of the active metal in the metal organic ligand catalyst to the molecular sieve catalyst is 1: (1-10); The metal organic ligand catalyst has a general formula of: 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 ligand, a represents the molar ratio of the non-coordinating oxygen atom linked 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 C3-C19 hydrocarbon group; x is 1, 2 or 3; a is a positive number of 1-5; b is a positive number of 0.5-3.

5.

2. The composite catalyst of claim 1, wherein, The content of the active metal in the metal organic ligand catalyst is 2-50% by weight based on the dry base weight of the metal organic ligand catalyst; The content of the molecular sieve active component in the molecular sieve catalyst is 10-50% by weight based on the dry base weight of the molecular sieve catalyst; The molar ratio between the active metal and the organic ligand in the metal organic ligand catalyst is 1: (0.5-3.5).

3. The composite catalyst of claim 2, wherein, The content of the active metal in the metal organic ligand catalyst is 10-30% by weight based on the dry base weight of the metal organic ligand catalyst; The molar ratio between the active metal and the organic ligand in the metal organic ligand catalyst is 1: (1.5-3).

4. The composite catalyst of claim 1, wherein, R is C5-C11 normal or isomeric alkyl group, C5-C12 ring-containing alkyl group and C6-C12 aryl group; x is 1 or 2; a is a positive number of 1-3; b is a positive number of 1.5-3.

5. The composite catalyst of claim 1, wherein, The molecular sieve catalyst can optionally comprise a matrix and a binder; the matrix is one or more of Al2O3, kaolin, amorphous aluminum silicate and white clay; the binder is one or more of silica-alumina sol, silica sol and aluminum sol; The content of the matrix in the molecular sieve catalyst is 0-70% by weight based on the dry base weight of the molecular sieve catalyst; the content of the binder is 0-50% by weight.

6. The composite catalyst of claim 1, wherein, The organic ligand is C4-C20 organic carboxylic acid and / or C4-C20 anhydride of the organic carboxylic acid, the organic carboxylic acid is one or more of C4-C20 normal or isomeric alkyl carboxylic acid, C6-C20 ring-containing saturated carbocyclic ring alkyl carboxylic acid and C7-C20 ring-containing aromatic carboxylic acid.

7. The composite catalyst of claim 6, wherein, The organic carboxylic acid is one or more of C4-C12 normal or isomeric alkyl carboxylic acid, C6-C13 cycloalkane carboxylic acid containing saturated carbon ring and C7-C13 aromatic carboxylic acid containing aromatic ring.

8. The composite catalyst of claim 1, wherein, The VB group metal, VIB group metal, VIII group metal, IB group metal and II B group metal are one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn.

9. The composite catalyst of claim 8, wherein, The VB group metal, VIB group metal, VIII group metal, IB group metal and II B group metal are one or more of Mo, Ni and Co.

10. A process for the preparation of the composite catalyst according to any one of claims 1 to 9, characterized in that, The method comprises: 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) in terms of metal.

11. The method of claim 10, wherein, The method further comprises: mixing an active metal precursor with an organic carboxylic acid to perform a complexation 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).

12. The method of claim 11, wherein, The active metal precursor is one or more of soluble molybdenum-containing compound, nickel-containing compound and cobalt-containing compound; The organic carboxylic acid is one or more of C4-C12 normal or isomeric alkyl carboxylic acid, C6-C13 cycloalkane carboxylic acid containing saturated carbon ring and C7-C13 aromatic carboxylic acid containing aromatic ring; The reaction temperature of the complexation reaction is 150-350℃, and the reaction time is 2-8h.

13. The method of claim 12, wherein, The active metal precursor is one or more of ammonium heptamolybdate, ammonium molybdate, molybdic acid, nickel hydroxide and cobalt nitrate.

14. A hydrocracking process for oil products, characterized by, The method comprises: Under the condition of hydrogenation reaction, the oil product raw material is contacted with the composite catalyst of any one of claims 1-9, pre-mixed, then enters a slurry bed reactor to contact with hydrogen and perform hydrocracking and upgrading reaction.

15. The method of claim 14, wherein, The oil product raw material comprises one or more of crude oil, gasoline, diesel, wax oil, residual oil, asphalt, coal tar, catalytic cracking oil slurry and biomass oil; The oil product raw material comprises 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 reforming reaction include: the amount of the metal organic ligand catalyst in the composite catalyst is 50-10000 μg / g, based on the weight of the oil product raw material; the amount of the molecular sieve catalyst is 50-100000 μg / g; the initial hydrogen pressure is 1-20 MPa; the reaction temperature is 300-500℃; the liquid hourly space velocity is 0.05-5.0 h -1 ; and the hydrogen-oil volume ratio is 100-3000.

16. The method of claim 15, wherein, The conditions of the hydrocracking and reforming reaction include: the amount of the metal organic ligand catalyst in the composite catalyst is 50-3000 μg / g, based on the weight of the oil feedstock; the amount of the molecular sieve catalyst is 50-30000 μg / g; the initial hydrogen pressure is 3-15 MPa; the reaction temperature is 350-450℃; the liquid hourly space velocity is 0.05-1.0 h -1 ; and the hydrogen to oil volume ratio is 200-2000.

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