CN114471719A - Hydrofining catalyst based on modified aluminum-based MOFs material and preparation method thereof - Google Patents
Hydrofining catalyst based on modified aluminum-based MOFs material and preparation method thereof Download PDFInfo
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- CN114471719A CN114471719A CN202011163464.6A CN202011163464A CN114471719A CN 114471719 A CN114471719 A CN 114471719A CN 202011163464 A CN202011163464 A CN 202011163464A CN 114471719 A CN114471719 A CN 114471719A
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- Prior art keywords
- catalyst
- preparation
- roasting
- aluminum
- mofs material
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
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- 239000004033 plastic Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
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- 230000004048 modification Effects 0.000 description 17
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- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a hydrofining catalyst based on modified aluminum-based MOFs materials and a preparation method thereof. The hydrofining catalyst prepared by the method can realize ultra-deep hydrodesulfurization and hydrodenitrogenation, optimize the pore structure of the catalyst and improve the industrial long-period stability of the catalyst.
Description
Technical Field
The invention relates to a hydrofining catalyst, in particular to a hydrofining catalyst based on a modified aluminum-based MOFs material and a preparation method thereof.
Background
With increasingly strict quality standards of gasoline, diesel and diesel oil executed in China, the hydrotreater of a refinery is very popular at present. The hydrorefining catalyst is used as the core of the hydrotreatment device, the activity of the hydrorefining catalyst directly affects the quality of the product of the hydrotreatment device, and the energy consumption and the material consumption of a refinery are also affected. At present, the development of a high-activity hydrofining catalyst becomes a hot spot of the industry, and the development of the high-activity hydrotreating catalyst mainly comprises the preparation of a carrier, the research of an active phase and the like. Through literature research and experimental research, a material called MOFs, i.e., Metal-Organic Frameworks (Metal-Organic Frameworks), has attracted considerable attention in recent years. The material is a crystal material with a periodic network structure formed by self-assembly by utilizing metal-ligand complexation between organic ligands and metal ions. MOFs materials show potential application prospects in the fields of gas storage and separation, sensors, catalysis and the like due to low-density pore structures, high specific surfaces and large adjustable porosity. At present, research reports of aluminum-based MOFs materials used for hydrofining catalysts exist, but no research reports related to hydrofining catalysts based on modified aluminum-based MOFs materials exist.
The synthesis of MOFs has received much attention from researchers over the last two decades, and by preparing a variety of MOFs with novel structures, novel materials showing excellent properties in the field of porous material applications can be found. The application fields of the material not only cover the traditional fields of gas storage, separation, catalysis and the like which are influenced by the pore structure and the interaction between host and guest molecules, but also include recently-developed bimetallic materials and sensor materials. In addition to the need of designing the geometric configuration of the product, the more important objective of MOFs synthesis is to find out appropriate reaction conditions so that the inorganic secondary structural unit and the organic ligand establish a coordination bond with strong interaction, and the structure and function of the organic ligand can be maintained, and simultaneously the crystal kinetic conditions of nucleation and growth of a specific crystal phase need to be satisfied. Different synthesis methods have great influence on the yield, the particle size and the morphology of reaction products, and different MOFs materials can be obtained by using the same reactant and only changing the synthesis method.
An aluminum-based organic framework material (Al-based MOFs, abbreviated as Al-MOFs) is an ideal porous material, and octahedrons with aluminum as a center can form various one-dimensional and two-dimensional inorganic secondary structural units, and are connected by organic ligands to form Al-MOFs with various types, structures and combinations. The research shows that the aluminum-based organic framework material has the most outstanding characteristics of high thermal stability and chemical stability, no toxicity and large specific surface area. Al-MOFs mainly adopts organic carboxylic acid ligands for synthesis, such as terephthalic acid, trimesic acid, naphthalenedicarboxylic acid and the like, and functional groups, such as hydroxyl, nitro, methyl, halogen and the like, can be introduced for modification of channels, and the modified MOFs channels can generate interaction with guest molecules, so that the performance is improved. Under the guidance of the controllable design of metal-organic framework materials, the types of Al-MOFs are continuously expanded, the functions are continuously improved, the application is also excavated, and a huge family is formed.
The preliminary work on Al-MOFs is mainly done by the researchers in professor F rey of Lawa Sn research Institute at Versailles university, and the MOFs of different structures researched are named as MIL-numbers (Materials of Institute Lavoiser). Solvothermal synthesis of aluminum terephthalic acid (BDC) salt MIL-53[ Al (OH) (BDC) ]was first reported in 2003]Later, aluminum-based organic framework materials have entered a vigorous development phase. Al-doped material with the same topological structure as MIL-53 is prepared by using 2, 6-naphthalenedicarboxylic acid as organic ligand through similar topological synthesisMOFs, named MIL-69[ Al (OH) (2, 6-NDC). H2O)]。
The aluminum-based organic framework material serving as a porous material not only has large specific surface area and open pore channels, but also has the advantages of being superior to other metal MOFs, such as hydrothermal preparation, no toxicity/low toxicity, stability to water (and water vapor) and the like. Especially, the service life of the Al-MOFs can be prolonged by keeping the stability in water vapor, and the application range of the Al-MOFs is expanded. In addition to the modularized structure and designable characteristics, the Al-MOFs can meet the fields of adsorption, separation, purification, catalysis and the like which have specific requirements on pores. In recent years, researchers have also explored the application fields of Al-MOFs, mainly relating to gas purification, gas separation, gas storage and catalysis.
The aluminum-based organic framework material is very suitable for being applied to the field of catalysis due to large specific surface area, proper pore structure, controllable synthesis and functional modification. The material can be used for heterogeneous catalysts, and can also be used as a catalyst carrier by utilizing the large specific surface area and rich pore channels of the material.
The carrier is used as an important component of the catalyst, plays a role in loading active components, providing a reaction site and playing a role in framework support. Among the supports which have been investigated so far are gamma-Al2O3、TiO2Activated carbon, zeolite, mesoporous molecular sieve, etc., wherein gamma-Al2O3Because of the factors of proper pore structure, higher mechanical strength, good regeneration performance, better thermal stability, low price and the like, the industrial hydrodesulfurization aromatic hydrocarbon saturated hydrocarbon catalyst often adopts gamma-Al2O3As a carrier. It is believed that the interaction between the support and the metal component primarily affects the degree of dispersion and sulfidability of the active metal component. The weak interaction is beneficial to the complete vulcanization of the catalyst, so the reaction activity is higher. However, in the case of Mo-based catalyst,. gamma. -Al2O3Is not an inert carrier, and strong interaction is generated between the carrier and Mo through basic hydroxyl groups on the surface of the carrier. gamma-Al2O3This strong interaction with the transition metal is detrimental to the HDS and HDAr reactions, depending on the preparationThe accessory, Ni and Co and other auxiliary ions can interact with the carrier and occupy the octahedral coordination or the tetrahedral coordination of the outer surface of the carrier, even form NiAl2O4Or CoAl2O4Spinel structure, which affects the activity of the catalyst. But at the same time, the strong interaction of the active component and the carrier is beneficial to the stability of the active component in the reaction process, the dispersion of the active component on the surface of the carrier and the re-dispersion of the active component in the regeneration process, and the formation of an active phase Mo-Co-S (I) is promoted. Due to gamma-Al2O3The carrier has strong Lewis acid center, which is beneficial to improving the hydrogenation activity, but also leads the surface of the catalyst to be easy to coke and deactivate, and reduces the service life of the catalyst.
The component which is added in a small amount to the carrier but can greatly improve the performance of the hydrogenation catalyst is called an auxiliary, and the activity, selectivity, activity stability, thermal stability and the like of the catalyst can be improved, and the research on the modification of the carrier will be discussed below.
Modification of titanium with conventional Al2O3In contrast, some oxides (e.g. TiO)2，ZrO2) Has high hydrogenation activity, but the defects of small specific surface area and pore volume, low mechanical strength, poor thermal stability and the like of the catalyst itself make it very difficult to directly use the catalyst as a carrier, and in order to make up for the defects, TiO is used in recent years2And Al2O3Making TiO in various ways2-Al2O3The research of composite carrier (TA) and the like becomes a hot spot. In TiO2-Al2O3The above is mainly expressed in an octahedral coordination form, which indicates that Al is present2O3The surface is covered with a layer of TiO2The concentration of the active Mo species can be increased, thereby effectively improving the hydrodesulfurization activity. Simultaneous TiO 22For Al2O3Surface covering weakenable MoO3With carrier Al2O3The interaction of (a).
In the research of Zn modified carrier, Zn can influence the acidity of the carrier, so that the dispersion degree of active components on the carrier can improve the activity of the catalyst. Camdra et al add Zn to a Mo-Co catalystCo is displaced from the tetrahedral active sites, promoting the formation of the CoMoS phase, increasing HDS activity. To increase W-Ni/Al2O3HDN activity of the catalyst, introduction of Zn and Mg into Al2O3In the carrier, Ni is suppressed2+To Al2O3And (4) diffusion. Method for investigating Ni by using ultraviolet-visible light diffuse reflection spectrum and X-ray diffraction measurement unit cell constant2+Coordination of (5) and NiAl2O4Formation of spinel Structure
The alkali metal modification, as shown by Venezia et al research on amorphous silica-alumina supported Mo-Co catalyst, Na content is increased from 0 wt% to 3.2 wt%, and the activity of the catalyst on thiophene HDS is increased along with the increase, and finally reaches the maximum value, because the introduction of sodium promotes the activity of Mo-Co-S phase precursor beta-CoMoO4The reason for this is that. Parola et al, on study with SiO2When the Mo-Co catalyst is used as a carrier, the strong electron donating capability of alkali metal leads the electron density of Co and Mo species center to be increased, which is beneficial to reduction, can improve the HDS activity of the catalyst on thiophene and reduce the carbon deposition rate.
Phosphorus is modified, and phosphorus (P) is used as an important auxiliary agent of the hydrogenation catalyst, so that the surface electrochemical property and surface acidity of the catalyst can be improved, the carbon deposition speed on the catalyst is reduced, the pore volume and specific surface area of the carrier alumina are improved, and the long-period stable operation of the catalyst is facilitated. P is mainly in the form of aluminium phosphate in Mo-Co/Al2O3In the presence of a catalyst, and gamma-Al2O3When the carrier is treated with phosphoric acid, a structure similar to AlPO4 formula is formed on the surface of the carrier, thereby suppressing the formation of Mo-O-Al and allowing molybdenum to be MoO3Exist in the form of (1). While the Co and phosphoric acid on the carrier will be in gamma-Al2O3The surface forms a structure similar to a cobalt phosphate type structure, so that Co is dispersed more uniformly.
Silicon modification, silica modification is a commonly used alumina modification method. Silica is a commonly used catalyst support, but numerous studies have shown that it has relatively low catalytic activity for hydroprocessing as a support. Due to SiO2Has the advantages of
Acid and Lewis acid, and SiO2Low isoelectric point (1.8-2.2), and Al2O3The isoelectric point is between 7 and 8, so SiO is adopted2For Al2O3Modification can reduce the interaction between the support and the metal active phase and can also improve Al2O3Strength and thermal stability. Compared with alumina, the silicon-containing alumina has the characteristics of small crystal grain, good thermal stability, large specific surface area and pore volume, centralized pore distribution, strong acidity, contribution to dispersion of active components and the like, and plays an important role in the development of distillate oil hydrofining catalysts. Leyva and the like use aluminum nitrate and sodium silicate as raw materials and NH3·H2O is used as a precipitator, and Al with different silicon contents is prepared by adopting a sol-gel homogeneous coprecipitation method2O3-SiO2Support [ Si/(Si + Al) ═ 0.06, 0.12, 0.31, 0.56, 0.78]The NiMo catalyst is prepared by adopting the co-impregnation liquid of nickel nitrate and ammonium hexamolybdate, and Al is researched2O3-SiO2Carrier composition paired catalyst MoS2And the degree of dispersion of the Ni-S phase and the activity of the thiophene HDS. The research result shows that SiO is added2Can improve Al after the treatment2O3Interaction of the carrier with the metal sulphide phase. The specific surface area of the carrier is increased from 376m with the increase of the Si content from 0.06 to 0.782The/g is reduced to 120m2The pore volume is firstly 0.55cm3Increase in g to 0.76cm3(ii)/g, wherein the pore volume is maximal at a Si content of 0.56; MoO3Crystal grains and MoS2The layer increases with increasing Si content, resulting in a decrease in catalyst activity.
In conclusion, the addition or introduction of the auxiliary agent into the carrier regulates the pore structure and acidity of the carrier. Meanwhile, the distribution of the metal components in the carrier can be improved, the interaction between the carrier and the metal active components can be modulated, more hydrogenation active centers are formed, and the hydrodesulfurization aromatic saturation activity of the catalyst is improved.
CN 200410091490.7 discloses a hydrodesulfurization catalyst containing a molecular sieve, wherein a carrier of the catalyst is prepared by adopting alumina (20.0 wt% -80.0 wt% of the weight of the catalyst) and an ETS-10 molecular sieve (0.5 wt% -50.0 wt% of the weight of the catalyst), and the desulfurization activity of a conventional hydrodesulfurization catalyst can be improved by adjusting the relative content of the alumina and the ETS-10 molecular sieve in the carrier and modifying the ETS-10 molecular sieve to prepare a hydrodesulfurization catalyst carrier.
CN 105772109 a discloses a method for preparing a carrier, which comprises the following steps: firstly, carrying out ammonium nitrate contact exchange on a small-particle Y molecular sieve with a high silica-alumina ratio; then carrying out zirconium modification on the exchanged Y molecular sieve to obtain a zirconium modified Y molecular sieve; mixing the zirconium modified Y molecular sieve with pseudo-boehmite, extrusion aid and binder, extruding, drying and roasting to prepare the carrier of the hydrodesulfurization catalyst. The carrier of the hydrodesulfurization catalyst provided by the invention has the zirconium modified Y molecular sieve, and the hydrodesulfurization catalyst prepared by the carrier has high desulfurization activity and good desulfurization effect; and the hydrodesulfurization catalyst prepared by the carrier is used for hydrodesulfurization reaction, and the yield of diesel oil is over 100 percent.
CN 103480408A discloses a diesel distillate oil hydrogenation catalyst containing rare earth, and preparation and application thereof; the catalyst consists of a rare earth modified USY molecular sieve, amorphous silicon aluminum, macroporous aluminum oxide and a hydrogenation active component, wherein the hydrogenation active component is VIII group metal, the catalyst contains 5-60 wt% of the rare earth modified USY molecular sieve, 5-80 wt% of the amorphous silicon aluminum, 0.1-10 wt% of the VIII group metal and the balance of the macroporous aluminum oxide; the catalyst has better hydrogenation, isomerization and aromatic selectivity ring-opening activity, can obviously improve the cetane number, reduce the condensation point, improve the product quality and keep the diesel yield over 95 percent when processing FCC hydrofined diesel distillate oil under a milder reaction condition, improves the activity and the service life of the catalyst by adding rare earth elements, and is particularly suitable for the second-stage aromatic deep hydrogenation saturation and then selective ring-opening in the two-stage hydrogenation modification of the diesel.
CN 102284300A discloses a poor diesel oil hydrogenation catalyst and a preparation method thereof; the catalyst takes W-Mo-Ni-P as an active component, alkali metal, alkaline earth metal or rare earth metal as an auxiliary agent, silicon-aluminum as a carrier, and the alkali metal, the alkaline earth metal or the rare earth metal accounts for 0.2-10% by weight,WO35 to 25 percent of MoO38-20%, 2-9% of NiO, 1.0-5% of P and the balance of a silicon-aluminum oxide carrier; the catalyst is used for evaluating the mixed oil of catalytic cracking and coking diesel oil as raw material oil, shows good reaction activity and stability in condition and stability tests, and can remove more than 90 percent of sulfur and nitrogen in inferior mixed diesel oil.
CN 102211029A discloses a preparation method of a diesel hydrodesulfurization sulfide catalyst, which takes metal Ni or Co, Mo and Ru as active components and Al2O3Preparing an ethylenediamine solution of ammonium molybdate as a carrier, adding the carrier for soaking, adding a 0.1mol/L KBH4 solution, wherein the molar ratio of Mo to B is 1: 4, washing the obtained precipitate with water, and drying in a 110 ℃ oven to obtain a catalyst precursor; preparing mixed solution of nickel nitrate and ruthenium nitrate, adding catalyst precursor into the mixed solution for isovolumetric impregnation, naturally drying the obtained precipitate, drying at 120 ℃, roasting at 450 ℃, and calcining at H2Sulfurizing at 350 deg.C under S atmosphere to obtain catalyst; mo accounts for 3-20% of the weight ratio of the catalyst; 3-10% of Ni or Co; ru is 0.1-3%; al (Al)2O3The balance is; the catalyst has high hydrodesulfurization activity and is used for hydrofining and raw material pre-refining hydrodesulfurization.
CN200810113646.5 discloses a diesel hydrorefining catalyst, which is composed of a carrier and an active component, wherein the active component is one or more of VIB group metals and VIII group metals, the carrier is composed of one or more of SAPO-5, SAPO-11, ZSM-22 and ZSM-23 molecular sieves with one-dimensional pore canals and gamma-Al2O3And (4) forming. The invention also discloses a preparation method of the catalyst on the basis of disclosing the diesel hydrofining hydrogenation catalyst. The diesel oil hydrofining catalyst prepared by the preparation method can effectively realize desulfurization and denitrification of poor diesel oil while preventing cracking of diesel oil fractions and realizing aromatic hydrocarbon hydrofaturation of the poor diesel oil.
CN200910188174.4 discloses a bulk phase ultra-deep hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises composite oxides NixWyOz and MoO3Alumina and microporous and mesoporous composite molecular sieves. Adding a proper amount of water-soluble nitrogen-containing compound in the process of Ni, W and Al precipitation, gelling, adding composite molecular sieve slurry, aging, and mixing with MoO3Pulping, molding and activating to obtain the product. The method not only improves the pore structure of the catalyst, exposes more metal active sites on the surface of the catalyst and improves the utilization rate of active metals, but also ensures that the composite molecular sieve is uniformly and fully contacted with hydrogenation active metals and is better matched with the hydrogenation active metals, fully exerts the performance of the composite molecular sieve, achieves the effect of ultra-deep desulfurization of diesel oil, has more obvious effect particularly when treating distillate oil with more macromolecule content, and can reduce the sulfur content of the diesel oil to be below 10 mu g/g.
ZL 201110197778.2 discloses a method for preparing a catalyst carrier having through-going large and medium pores, which comprises: adding solid fiber yarns in the preparation or forming process of the catalyst carrier to disperse the solid fiber yarns in the catalyst carrier, and then removing the solid fiber yarns through forming and roasting to obtain the catalyst carrier with through large and medium pores. The invention also provides a method for preparing a catalyst by further loading active components on the carrier, and also provides the carrier and the catalyst prepared by the method. By using the method of the invention, the penetration performance of the pore canal in the carrier is greatly improved by adding the solid fiber filaments. The through macropores generated by the fiber filaments provide a rapid diffusion channel for reaction molecules, so that the mass transfer resistance in the catalytic reaction process is reduced. The process is suitable for preparing various catalysts whose reaction rate is controlled by internal diffusion, such as hydrogenation catalysts for petroleum fractions (especially heavy oil fractions).
MIL-101(Al)-NH2Acts as a highly reactive base catalyst in the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate. The catalyst can be reused without reducing the activity, and the product can reach high conversion rate even if the catalyst is reacted in a non-polar solvent. Garibay et Al studied MIL-53(Al) -NH2After a series of cyclic anhydride modification, the catalytic effect on alcoholysis reaction of certain small molecular epoxy compounds is achieved,through comparison, the MIL-53(Al) -AMMal functionalized by maleic acid serves as a B acid site in the catalyst, the alcoholysis of epoxy compounds is promoted, the monopoly of the traditional homogeneous acid catalyst is broken, the catalyst can be recycled after being regenerated, and the activity is basically not lost. The catalytic properties of MIL-53(Al) -AMMal, although highly selective, do not work with all epoxy systems.
The above-mentioned patent publications respectively utilize different preparation methods and modification methods to prepare the hydrorefining catalyst, and adopt conventional alumina or molecular sieve as carrier, and the modifier mainly can change pore size distribution and surface property of carrier. The hydrofining catalyst modified based on the modified aluminum-based MOFs material is very suitable for being applied to the field of catalysis due to the large specific surface area, the proper pore structure, controllable synthesis and functional modification.
Disclosure of Invention
The technical problem to be solved by the invention is how to improve the activity of the hydrofining catalyst.
In order to solve the problems, the method provided by the invention is mainly based on the aluminum-based MOFs material which has large specific surface area, proper pore structure and controllable synthesis and functional modification, and the aluminum-based MOFs material is modified and treated, and part of the modified aluminum-based MOFs material is mixed in the alumina carrier, so that the effect of improving the pore structure and the surface property of the hydrofining catalyst carrier is achieved, and the hydrofining catalyst with high activity is prepared.
The preparation method mainly comprises the preparation of the modified aluminum-based MOFs material, the preparation of a hydrofining catalyst carrier and an active component, and the preparation and activation processes of the hydrofining catalyst.
The transition metal contains empty orbitals, so that the transition metal is more easily coordinated with organic ligands to form a metal-organic framework material compared with main group metals, and thus MOFs materials taking the transition metal as a node are more diverse in topological structure and variety than main group metal MOFs. Al-MOFs is mainly synthesized by adopting organic carboxylic acid ligands, such as terephthalic acid, trimesic acid, naphthalene dicarboxylic acid and the like, and functional groups, such as hydroxyl, nitro, methyl, halogen and the like, can be introduced to modify the channels, and the modified MOFs channels can generate interaction with object molecules, so that the performance is improved. Under the guidance of the controllable design of metal-organic framework materials, the types of Al-MOFs are continuously expanded, the functions are continuously improved, the application is also excavated, and a huge family is formed. Thus, modifications to aluminum-based MOFs materials are feasible.
The invention provides a preparation method of a hydrofining catalyst based on a modified aluminum-based MOFs material, which is characterized by comprising the following preparation steps of: (1) preparing a modified aluminum-based MOFs material: and uniformly mixing the aluminum-based MOFs material with one or more of titanium oxide, nano-silica, silica sol, zirconia, boric acid or metatitanic acid, and carrying out hydrothermal treatment on the mixed mixture to obtain the modified aluminum-based MOFs material. (2) Preparation of catalyst carrier: uniformly mixing pseudo-boehmite powder, a modified aluminum-based MOFs material, a peptizer and a forming aid, adding deionized water and nitric acid, kneading in a kneader to form a plastic soft block, putting the plastic soft block into a material groove of a strip extruding machine, extruding strips and cutting into granules through a clover-shaped pore plate, and then curing, drying and roasting to obtain a clover-shaped carrier; (3) preparation of an impregnation liquid: adding a certain amount of phosphoric acid into deionized water, uniformly stirring, adding one or two of active component salts into a phosphoric acid aqueous solution, fully stirring to completely dissolve active component metal salts, and continuously adding deionized water to the volume of the prepared solution to obtain a co-impregnation solution of the active components; (4) preparing a catalyst: and (3) placing the cloverleaf alumina carrier prepared in the step (2) into an impregnation tank, adding the impregnation liquid prepared in the step (3) to obtain a catalyst wet strip, and carrying out health preserving, drying and roasting to obtain the cloverleaf hydrofining catalyst.
Preparing a modified aluminum-based MOFs material: the preferred aluminum-based MOFs material is any one or a combination of MIL-53(AI), MIL-96(AI), MIL-100(AI) or MIL-110 (AI); the modifier is one or more of titanium oxide, nano-silica, silica sol, zirconium oxide, boric acid or metatitanic acid; the mass ratio of the modifier to the aluminum-based MOFs material is 0.03-0.2: 1; the preferable conditions of the hydrothermal treatment are as follows: the pressure is 0.3-0.4 MPa, the temperature is 450-750 ℃, and the treatment time is 3-8 hours; the roasting condition is 500-600 ℃, and the treatment time is 2-6 hours.
Preparation of catalyst carrier: the mass ratio of the modified aluminum-based MOFs material to the pseudo-boehmite powder is 0.01-0.15, and the mixture of the modified aluminum-based MOFs material and the pseudo-boehmite powder is hereinafter referred to as powder; the mass ratio of the peptizing agent to the powder is 0.015-0.04; the mass ratio of the forming aid to the powder is 0.02-0.05, and the mass ratio of the nitric acid to the powder is 0.01-0.2. The peptizing agent is one or a mixture of citric acid, tartaric acid, oxalic acid, ethylenediamine tetraacetic acid and the like; the forming auxiliary agent is one or a mixture of sesbania powder, methyl cellulose, carbon black and the like; the curing, drying and roasting conditions of the formed carrier are as follows: preserving at room temperature for 2-4 h, drying at 100-150 ℃ for 2-6 h, and roasting at 400-600 ℃ for 4-8 h.
Preparation of the catalyst: the catalyst curing, drying and roasting conditions in the step (4) are as follows: preserving at room temperature for 2-10 h, drying at 100-150 ℃ for 2-6 h, and roasting at 400-600 ℃ for 2-10 h.
The invention also provides a hydrofining catalyst based on the modified aluminum-based MOFs material, which is prepared by the preparation method, and comprises 0-10 wt% of cobalt oxide, 5-20 wt% of molybdenum oxide, 0-10 wt% of nickel oxide, 10-25 wt% of tungsten oxide, 0-10 wt% of phosphorus pentoxide, 5-20 wt% of titanium dioxide and 5-20 wt% of silicon dioxide, wherein the total weight of the hydrofining catalyst is taken as a reference.
The hydrofining catalyst is suitable for petroleum fraction hydrotreating with a distillation range of 40-390 ℃, adopts a single-stage single-agent process flow, and has the advantages that the reaction temperature is 240-390 ℃, the hydrogen partial pressure is 0.5-12.0 MPa, the hydrogen-oil volume ratio is 80-500: 1, and the liquid hourly volume space velocity is 1.0-8.0 h under the condition of the presence of hydrogen after the catalyst is vulcanized-1。
Compared with the prior art, the invention develops the hydrofining catalyst of the modified aluminum-based MOFs material and the preparation method thereof, the catalyst adopts the modification treatment on the aluminum-based MOFs material, the modification treatment mode is simple and practical, the modified aluminum-based MOFs material is mixed with the conventional alumina material to obtain the catalyst carrier with improved pore structure and surface property, the pore structure and the surface chemical property of the hydrofining catalyst are improved, and the hydrogenation activity and the stability of the catalyst are further improved; compared with other catalysts, the hydrofining catalyst has the characteristics of high activity, stable performance, strong coking resistance and wide raw material treatment range. The method has the advantages of simplicity, easy implementation, remarkable effect after implementation and the like.
Detailed Description
The invention provides a hydrofining catalyst based on modified aluminum-based MOFs material and a preparation method thereof, and the catalyst is mainly prepared by mixing the modified aluminum-based MOFs material with conventional alumina to prepare a hydrofining catalyst carrier with excellent performance by means of modification treatment of the aluminum-based MOFs material which has large specific surface area, proper pore structure, controllable synthesis and functional modification. To further illustrate the present invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1:
100g of aluminum-based MOFs material MIL-53(AI), 3g of titanium dioxide, 1g of metatitanic acid and 2g of phosphoric acid are fully and uniformly mixed, and then the mixture is put into a hydrothermal device for hydrothermal treatment, wherein the pressure is set to be 0.3MPa, the temperature is 450 ℃, and water vapor is introduced into the hydrothermal device, and the treatment time is 3 hours. And roasting the treated mixed sample in a muffle furnace at 500 ℃ for 2 hours to obtain the modified aluminum-based MOFs material, and recording the modified aluminum-based MOFs material as a sample 1.
Example 2:
50g of aluminum-based MOFs material MIL-96(AI), 50g of aluminum-based MOFs material MIL-100(AI), 3g of nano-silica, 17g of silica sol (the content of the silica is 30wt percent) and 5g of phosphoric acid are mixed fully and uniformly, and then the mixture is put into a hydrothermal device for hydrothermal treatment, wherein the pressure is set to be 0.4MPa, water vapor is introduced under the condition that the temperature is 750 ℃, and the treatment time is 8 hours. And roasting the treated mixed sample in a muffle furnace at 600 ℃ for 6 hours to obtain the modified aluminum-based MOFs material, and recording the modified aluminum-based MOFs material as a sample 2.
Example 3:
100g of aluminum-based MOFs material MIL-110(AI), 5g of zirconia and 10g of boric acid are fully and uniformly mixed, and then the mixture is put into a hydrothermal device for hydrothermal treatment, wherein the pressure is set to be 0.35MPa, the temperature is 550 ℃, and steam is introduced into the hydrothermal device for 5 hours. And roasting the treated mixed sample in a muffle furnace at 550 ℃ for 4 hours to obtain the modified aluminum-based MOFs material, and recording the modified aluminum-based MOFs material as a sample 3.
Example 4:
mechanically mixing 100g of commercial pseudo-boehmite, 1g of sample 1, and 5g of sesbania powder for 30 min; 3g of citric acid is dissolved in 80g of deionized water, 15g of nitric acid with the concentration of 68% is added, and the mixture is added into the uniformly mixed powder and wet mixed for 35min to prepare the plastic soft block. Adding the prepared plastic soft block into a trough of a strip extruding machine, extruding by using a clover-shaped orifice plate, and granulating to obtain the clover-shaped carrier. And then curing at room temperature for 2 hours, drying at 120 ℃ for 4 hours in an air atmosphere, placing in a muffle furnace at 450-550 ℃, and roasting in the air atmosphere for 4 hours to obtain the hydrofining catalyst carrier 1.
Example 5:
mechanically mixing 100g of commercial pseudo-boehmite, 15g of sample 2, 3g of sesbania powder and 2g of methylcellulose for 30 min; dissolving 2g of citric acid and 2g of tartaric acid in 80g of deionized water, adding 15g of nitric acid with the concentration of 68%, adding the nitric acid into the uniformly mixed powder, and wet-mixing for 35min to obtain the plastic soft block. Adding the prepared plastic soft block into a trough of a strip extruding machine, extruding by using a clover-shaped orifice plate, and granulating to obtain the clover-shaped carrier. And then curing at room temperature for 2 hours, drying at 120 ℃ for 4 hours in an air atmosphere, placing in a muffle furnace at 450-550 ℃, and roasting in the air atmosphere for 4 hours to obtain the hydrofining catalyst carrier 2.
Example 6:
mechanically mixing 100g of commercial pseudo-boehmite, 10g of sample 3, 2g of sesbania powder and 3g of carbon black for 30 min; dissolving 1g of citric acid and 2g of oxalic acid in 80g of deionized water, adding 15g of nitric acid with the concentration of 68%, adding the nitric acid into the uniformly mixed powder, and wet-mixing for 35min to obtain the plastic soft block. Adding the prepared plastic soft block into a trough of a strip extruding machine, extruding by using a clover-shaped orifice plate, and granulating to obtain the clover-shaped carrier. And then curing at room temperature for 2 hours, drying at 120 ℃ for 4 hours in an air atmosphere, placing in a muffle furnace at 450-550 ℃, and roasting in the air atmosphere for 4 hours to obtain the hydrofining catalyst carrier 3.
Example 7:
adding 35g of phosphoric acid into 300g of deionized water, uniformly stirring, adding 85g of industrial molybdenum trioxide, 165g of industrial ammonium metatungstate and 210g of industrial nickel nitrate into a phosphoric acid solution, continuously stirring, heating to 90-100 ℃ after 40min, adding 120g of industrial cobalt nitrate, stirring for 20min, cooling to room temperature, and fixing the volume of the solution to 500ml to obtain impregnation liquid 1.
Example 8:
adding 50g of phosphoric acid into 300g of deionized water, uniformly stirring, adding 50g of industrial molybdenum trioxide, 105g of industrial ammonium metatungstate and 60g of industrial basic nickel carbonate into a phosphoric acid solution, continuously stirring, heating to 90-100 ℃ after 40min, adding 100g of citric acid and 75g of industrial cobalt nitrate, stirring for 20min, cooling to room temperature, and fixing the volume of the solution to 500ml to obtain impregnation liquid 2.
Example 9:
and (3) respectively taking 100g of the prepared hydrofining catalyst carriers 1, 2 and 3, placing the obtained hydrofining catalyst carriers in an impregnation tank, adding impregnation liquid 1, adopting equal-volume impregnation, impregnating for 40min, then carrying out curing for 2h at room temperature, drying for 4h at 120 ℃, placing the obtained product in a muffle furnace for 500 ℃, and roasting for 4h in an air atmosphere to obtain the hydrofining catalysts 1, 2 and 3.
Example 10:
and (3) respectively taking 100g of the prepared hydrofining catalyst carriers 1, 2 and 3, placing the obtained hydrofining catalyst carriers in an impregnation tank, adding impregnation liquid 2, adopting equal-volume impregnation, impregnating for 40min, curing at room temperature for 2h, drying at 120 ℃ for 4h, placing in a muffle furnace, curing at 500 ℃ for 4h in an air atmosphere, and preparing hydrofining catalysts 4, 5 and 6.
Example 11
In this example, the comparative hydrogenation evaluation was performed on the hydrofining catalysts 1, 2, 3, 4, 5, 6 and a comparative sample, which is a conventional hydrofining catalyst without adding a modified aluminum-based MOFs material.
The apparatus used was a 200mL small hydrogenation evaluation apparatus. 200mL of catalyst was charged into the reactor, and the temperature was gradually raised to 370 ℃ in a hydrogen atmosphere, and the reactor was purged with 2.0% CS2The catalyst is presulfurized by kerosene, and the vulcanization time is 40 h. The mass ratio of the raw oil to the straight-run diesel oil is 1:1, wherein the sulfur content is 7000 mu g/g, and the nitrogen content is 760 mu g/g. The reaction conditions are as follows: pressure 6.4MPa, temperature: 360 ℃, space velocity: 2.0h-1Hydrogen-oil volume ratio: 400: 1. the comparative evaluation results are shown in Table 1.
TABLE 1 comparison of the Performance of the catalysts in hydrodesulfurization reactions
The activity is expressed as relative activity, i.e. the activity of the corresponding untreated catalyst when it is operated for 200 hours is taken as 100, and the activity obtained by comparing the catalyst of the present invention with it represents the relative activity of the catalyst of the present invention. The relative desulfurization activity was calculated by the following formula:
relative desulfurization Activity 100 × [ (1/Sp)0.65-(1/Sf)0.65]/[(1/Spr)0.65-(1/Sfr)0.65]
In the formula, Sfr and Spr respectively represent the sulfur concentration of a diesel fraction used by a reference agent and a product subjected to hydrogenation treatment by the reference agent, and Sf and Sp respectively represent the sulfur concentration of a diesel fraction used by the catalyst and a product subjected to hydrogenation treatment by the catalyst.
Claims (12)
1. A preparation method of a hydrofining catalyst based on modified aluminum-based MOFs materials is characterized by comprising the following steps:
(1) preparing a modified aluminum-based MOFs material: uniformly mixing the aluminum-based MOFs material with a modifier to obtain a mixture, carrying out hydrothermal treatment on the mixture, and roasting to obtain a modified aluminum-based MOFs material;
(2) preparation of catalyst carrier: uniformly mixing pseudo-boehmite powder, a modified aluminum-based MOFs material, a peptizing agent and a forming aid, adding deionized water and nitric acid, kneading, extruding, cutting into granules, curing, drying and roasting to obtain a catalyst carrier;
(3) preparation of an impregnation liquid: adding active component salt into a phosphoric acid solution, fully stirring and dissolving, and adding deionized water to the volume of the prepared solution to obtain co-impregnation liquid of the active components;
(4) preparation of the catalyst: and (3) placing the catalyst carrier prepared in the step (2) into an impregnation tank, adding the co-impregnation liquid of the active component prepared in the step (3), and curing, drying and roasting to obtain the hydrofining catalyst based on the modified aluminum-based MOFs material.
2. The preparation method according to claim 1, wherein the aluminum-based MOFs material is at least one selected from the group consisting of MIL-53(AI), MIL-96(AI), MIL-100(AI) and MIL-110 (AI).
3. The production method according to claim 1, wherein the modifier is at least one selected from the group consisting of titanium oxide, nano-silica, silica sol, zirconium oxide, boric acid, and metatitanic acid.
4. The preparation method according to claim 1, wherein the mass ratio of the modifier to the aluminum-based MOFs material is 0.03-0.2: 1.
5. the preparation method according to claim 1, wherein in the step (1), the hydrothermal treatment is carried out under the conditions of pressure of 0.3 to 0.4MPa, temperature of 450 to 750 ℃ and treatment time of 3 to 8 hours; the roasting condition is that the temperature is 500-600 ℃, and the roasting time is 2-6 hours.
6. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the modified aluminum-based MOFs material to the pseudo-boehmite powder is 0.01-0.15; the mixture of the modified aluminum-based MOFs material and the pseudo-boehmite powder is powder, and the mass ratio of the peptizing agent to the powder is 0.015-0.04; the mass ratio of the forming aid to the powder is 0.02-0.05, and the mass ratio of the nitric acid to the powder is 0.01-0.2.
7. The preparation method according to claim 1, wherein the peptizing agent is one or more of citric acid, tartaric acid, oxalic acid, ethylenediamine tetraacetic acid and the like; the forming auxiliary agent is one or a mixture of sesbania powder, methyl cellulose, carbon black and the like.
8. The preparation method according to claim 1, wherein in the step (2), the curing condition is room temperature curing for 2-4 h; the drying temperature is 100-150 ℃, and the drying time is 2-6 h; the roasting temperature is 400-600 ℃, and the roasting time is 4-8 h.
9. The preparation method according to claim 1, wherein in the step (4), the curing condition is 2-10 h at room temperature; the drying time is 100-150 ℃, and the drying time is 2-6 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
10. The preparation method according to claim 1, wherein in the step (2), the kneading and extruding process comprises: kneading the mixture into plastic soft blocks in a kneader, putting the plastic soft blocks into a material tank of a strip extruding machine, extruding strips and cutting granules through a cloverleaf orifice plate, and then curing, drying and roasting to obtain a cloverleaf catalyst carrier; in the step (4), the hydrofining catalyst based on the modified aluminum-based MOFs material is in a clover shape.
11. A hydrofining catalyst based on modified aluminum-based MOFs materials, prepared by the preparation method of the hydrofining catalyst according to any one of claims 1 to 10, wherein the hydrofining catalyst comprises 0 to 10 wt% of cobalt oxide, 5 to 20 wt% of molybdenum oxide, 0 to 10 wt% of nickel oxide, 10 to 25 wt% of tungsten oxide, 0 to 10 wt% of phosphorus pentoxide, 5 to 20 wt% of titanium dioxide and 5 to 20 wt% of silicon dioxide, and the active components are based on the total weight of the hydrofining catalyst.
12. The hydrofining catalyst of claim 11, wherein the hydrofining catalyst is suitable for hydrotreating petroleum fractions with a distillation range of 40-390 ℃, a single-stage single-agent process is adopted, the hydrofining catalyst is vulcanized and then reacts in the presence of hydrogen, the reaction temperature is 240-390 ℃, the hydrogen partial pressure is 0.5-12.0 MPa, the hydrogen-oil volume ratio is 80-500: 1, and the liquid hourly volume space velocity is 1.0-8.0 h-1。
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