CN114471719B - 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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- CN114471719B CN114471719B CN202011163464.6A CN202011163464A CN114471719B CN 114471719 B CN114471719 B CN 114471719B CN 202011163464 A CN202011163464 A CN 202011163464A CN 114471719 B CN114471719 B CN 114471719B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 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
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000036541 health Effects 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
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- 239000003607 modifier Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
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- 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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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 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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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229910010413 TiO 2 Inorganic materials 0.000 description 4
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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- 150000001340 alkali metals Chemical class 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 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
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 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
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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Abstract
The invention discloses a hydrofining catalyst based on a modified aluminum-based MOFs material and a preparation method thereof. The hydrofining catalyst prepared by the method can realize ultra-deep hydrodesulfurization and hydrodenitrogenation, optimize the pore channel 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 the increasingly strict quality standards of gasoline, diesel and diesel oil executed in China, the hydrotreating device of a refinery is very popular at present. The hydrofining catalyst is used as the core of the hydrotreater, and the activity of the hydrofining catalyst directly influences the quality of the hydrotreater product and the energy consumption and the material consumption of a refinery. At present, the development of the high-activity hydrofining catalyst becomes a hotspot of the industry, and the development of the high-activity hydrofining catalyst mainly comprises the research of carrier preparation and active phase and the like. Through literature studies and experimental studies, it has been found that in recent years, a material called MOFs, namely Metal-organic frameworks (Metal-Organic Frameworks), has attracted great attention. The material is a crystal material with a periodic network structure formed by self-assembly by utilizing metal-ligand complexation between an organic ligand and a metal ion. MOFs material has potential application prospects in the fields of gas storage and separation, sensors, catalysis and the like due to low-density pore structures, high specific surface and large adjustable porosity. At present, research on using aluminum-based MOFs materials for hydrofining catalysts has been reported, but no research on hydrofining catalysts based on modified aluminum-based MOFs materials has been reported.
The synthesis of MOFs has received extensive attention from researchers over the last two decades, and by preparing a variety of MOFs with novel structures, novel materials can be discovered that exhibit excellent properties in the porous material application field. The application fields of the porous material not only cover the traditional fields of gas storage, separation, catalysis and the like which are affected by the interaction between a porous structure and a host and guest molecule, but also comprise bimetallic materials and sensor materials which are recently developed. In addition to the need for designing the geometry of the product, MOFs synthesis has the more important goal of finding suitable reaction conditions that allow the inorganic secondary building blocks to build strong interacting coordination bonds with the organic ligands, and that can maintain the structure and function of the organic ligands themselves, while also meeting the crystal kinetics conditions of nucleation and growth of specific crystalline phases. Different synthesis methods have great influence on the yield, particle size and morphology of reaction products, and different MOFs materials can be obtained by using the same reactant and changing the synthesis method.
An aluminum-based organic framework material (Al-based MOFs, abbreviated as Al-MOFs) is an ideal porous material, an octahedron with aluminum as a center can form various one-dimensional and two-dimensional inorganic secondary structural units, and the organic ligand is used for connecting the octahedron to form various types, structures and combinations of the Al-MOFs. The research shows that the aluminum-based organic frame material has the characteristics of high thermal stability, high chemical stability, no toxicity and large specific surface area. Al-MOFs are 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 pore channels, so that the modified MOFs have interaction with guest molecules, and the performance is improved. Under the guidance of controllable design of metal-organic framework materials, the types of Al-MOFs are continuously expanded, functions are continuously improved, applications are also excavated, and a huge family is being formed.
The earlier work of Al-MOFs is mainly completed by F erey professor of Lavaltin institute of Versailles university and researchers of subject group, and MOFs with different structures are respectively named as MIL-numbers (MATERIALS OF INSTITUTE LAVOISIER). After the first report of solvothermal synthesis of aluminum terephthalic acid (BDC) salt MIL-53[ Al (OH) (BDC) ] in 2003, aluminum-based organic framework materials entered the explosive stage of development. Al-MOFs with the same topological structure as MIL-53 is prepared by similar topological synthesis by taking 2, 6-naphthalene dicarboxylic acid as an organic ligand, and is named MIL-69[ Al (OH) (2, 6-NDC). H 2 O) ].
The aluminum-based organic framework material is used as a porous material, not only has large specific surface area and open pore channels, but also has advantages over 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 Al-MOFs stable in water vapor, and the application range of the Al-MOFs is expanded. The modular structure and the designable characteristic of the Al-MOFs can meet the fields of adsorption, separation, purification, catalysis and the like with specific requirements on pore channels. In recent years, researchers have also explored the field of application of Al-MOFs, mainly involving 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.
The carrier serves as an important component of the catalyst, acts as a load active component, provides a reaction site, and acts as a framework support. The currently studied carriers are gamma-Al 2O3、TiO2, active carbon, zeolite, mesoporous molecular sieve and the like, wherein gamma-Al 2O3 is used as a carrier for industrial hydrodesulfurization aromatic saturated hydrocarbon catalysts due to the factors of proper pore structure, high mechanical strength, good regeneration performance, good thermal stability, low price and the like. It is believed that the interaction between the support and the metal component is primarily responsible for the dispersion and sulfidability of the active metal component. The weak interaction is beneficial to complete vulcanization of the catalyst, so that the reaction activity is higher. However, gamma-Al 2O3 is not an inert support for Mo catalysts, and has a strong interaction with Mo through basic hydroxyl groups on the surface of the support. The strong interaction of gamma-Al 2O3 and transition metal is unfavorable for HDS and HDAr reactions, and auxiliary ions such as Ni and Co can interact with the carrier according to different preparation conditions to occupy the octahedral coordination or the tetrahedral coordination of the outer surface of the carrier, even form a NiAl 2O4 or CoAl 2O4 spinel structure, and influence the activity of the catalyst. But simultaneously, the strong interaction between 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 redispersion of the active component in the regeneration process, and the formation of an active phase Mo-Co-S (I) is promoted. Because the gamma-Al 2O3 carrier has a strong Lewis acid center, the catalyst surface is easy to coke and deactivate, and the service life of the catalyst is reduced, although the hydrogenation activity is improved.
The components which are added in small amounts to the carrier but which can greatly improve the performance of the hydrogenation catalyst are called assistants, and the activity, selectivity, activity stability, thermal stability and the like of the catalyst can be improved.
Titanium is modified, and compared with the traditional Al 2O3, some oxides (such as TiO 2,ZrO2) have high hydrogenation activity, but the titanium is difficult to be directly used as a carrier due to the defects of small specific surface area and pore volume, low mechanical strength, poor thermal stability and the like, so that in order to compensate the defects, the research of preparing TiO 2-Al2O3 composite carrier (TA) by using TiO 2 and Al 2O3 in various ways in recent years becomes a hot spot. The surface of Al 2O3 is covered with a layer of TiO 2, which is mainly expressed in an octahedral coordination form on TiO 2-Al2O3, so that the concentration of active Mo species can be increased, and the hydrodesulfurization activity can be effectively improved. At the same time, the TiO 2 can weaken the interaction of MoO 3 and the carrier Al 2O3 by covering the surface of Al 2O3.
In the research of Zn modified carrier, zn can influence the acidity of the carrier, so that the dispersity of active components on the carrier can be improved. Cambra et al add Zn to the Mo-Co catalyst to displace Co from tetrahedrally active sites, promoting formation of CoMoS phases and increasing HDS activity. To increase HDN activity of the W-Ni/Al 2O3 catalyst, zn and Mg were introduced into the Al 2O3 support, inhibiting Ni 2+ diffusion to Al 2O3. The coordination of Ni 2+ and the formation of the spinel structure of NiAl 2O4 were examined by methods such as diffuse reflection spectrum of ultraviolet and visible light and determination of unit cell constant by X-ray diffraction
As a result of the study of alkali metal modified Venezia et al on amorphous silica alumina supported Mo-Co catalysts, na content increased from 0wt% to 3.2wt%, and the HDS activity of the catalyst increased with it, eventually reaching a maximum, due to the sodium incorporation promoting the formation of the active Mo-Co-S phase precursor beta-CoMoO 4. Parola and the like, when researching a Mo-Co catalyst taking SiO 2 as a carrier, the strong electron donating ability of alkali metal leads to the increase of electron density of Co and Mo species centers, is beneficial to reduction, can improve the HDS activity of the catalyst on thiophene, and reduces the carbon deposition rate.
The phosphorus (P) is used as an important auxiliary agent of the hydrogenation catalyst, so that the surface electrochemical property and the surface acidity of the catalyst can be improved, the carbon deposition speed on the catalyst can be reduced, the pore volume and the specific surface area of the carrier alumina can be improved, and the long-period stable operation of the catalyst can be facilitated. P exists mainly in the form of aluminum phosphate in the Mo-Co/Al 2O3 catalyst, while when the gamma-Al 2O3 carrier is treated with phosphoric acid, a structure similar to the AlPO4 type is formed on the surface of the carrier, so that the generation of Mo-O-Al is inhibited, and molybdenum exists in the form of MoO 3. And Co and phosphoric acid on the carrier can form a cobalt phosphate-like structure on the surface of gamma-Al 2O3, so that Co is dispersed more uniformly.
Silicon modification, silica modification is a commonly used modification method for alumina. Silica is a commonly used catalyst support, but a number of studies have shown that the hydrotreating catalytic activity as a support is relatively low. Since SiO 2 hasThe acidity and Lewis acidity, the isoelectric point of SiO 2 is lower and is between 1.8 and 2.2, and the isoelectric point of Al 2O3 is between 7 and 8, so that the SiO 2 is adopted to modify Al 2O3, the interaction between a carrier and a metal active phase can be reduced, and the strength and the thermal stability of Al 2O3 can be improved. Compared with alumina, the silicon-containing alumina has the characteristics of small crystal grain, good heat stability, large specific surface area and pore volume, concentrated pore distribution, strong acidity, contribution to the dispersion of active components and the like, and plays an important role in the development of distillate oil hydrofining catalysts. Leyva and the like take aluminum nitrate and sodium silicate as raw materials, NH 3·H2 O as a precipitator, al 2O3-SiO2 carriers with different silicon contents [ Si/(Si+Al) =0.06, 0.12, 0.31, 0.56 and 0.78] are prepared by adopting a sol-gel homogeneous phase coprecipitation method, a NiMo catalyst is prepared by adopting nickel nitrate and ammonium hexamolybdate co-impregnation liquid, and the influence of Al 2O3-SiO2 carrier composition on the dispersity of MoS 2 and Ni-S phases of the catalyst and the HDS activity of thiophene is studied. The research result shows that the interaction between the Al 2O3 carrier and the metal sulfide phase can be improved after SiO 2 is added. As the Si content increases from 0.06 to 0.78, the specific surface area of the carrier decreases from 376m 2/g to 120m 2/g, the pore volume increases from 0.55cm 3/g to 0.76cm 3/g, and the pore volume is the largest when the Si content is 0.56; both the MoO 3 grains and the MoS 2 layer increase with increasing Si content, resulting in a decrease in catalyst activity.
In summary, the addition or introduction of an auxiliary agent to the support adjusts the pore structure and acidity of the support. Meanwhile, the distribution of the metal components in the carrier can be improved, the interaction between the carrier and the metal active components is modulated, more hydrogenated active centers are formed, and the saturation activity of the hydrodesulfurization aromatic hydrocarbon of the catalyst is improved.
CN 200410091490.7 discloses a hydrodesulfurization catalyst containing molecular sieve, the carrier of the catalyst is prepared by alumina (20.0 wt% -80.0 wt% of catalyst weight) and ETS-10 molecular sieve (0.5 wt% -50.0 wt% of catalyst weight), the desulfurization activity of conventional hydrodesulfurization catalyst can be improved by adjusting the relative content of alumina and ETS-10 molecular sieve in the carrier and modifying the ETS-10 molecular sieve.
CN 105772109A discloses a carrier preparation method which comprises the following steps: firstly, carrying out ammonium nitrate contact exchange on a small-particle Y molecular sieve with high silicon-aluminum 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, an extrusion aid and a binder, extruding strips, drying and roasting to prepare the carrier of the hydrodesulfurization catalyst. The carrier of the hydrodesulfurization catalyst provided by the invention is provided with a zirconium modified Y molecular sieve, and the hydrodesulfurization catalyst prepared by the carrier has high desulfurization activity and good desulfurization effect; 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 rare earth-containing diesel distillate hydrogenation catalyst, its preparation and application; the catalyst consists of a rare earth modified USY molecular sieve, amorphous silicon aluminum, macroporous alumina and a hydrogenation active component, wherein the hydrogenation active component is VIII family metal, the catalyst contains 5-60wt% of the rare earth modified USY molecular sieve, 5-80wt% of the amorphous silicon aluminum, 0.1-10wt% of the VIII family metal and the balance of the macroporous alumina; the catalyst has better hydrogenation, isomerization and arene selective ring opening activities, can obviously improve the cetane number, reduce the condensation point, improve the product quality, keep the diesel oil yield by more than 95 percent and improve the activity and the service life of the catalyst by adding rare earth elements under milder reaction conditions when the FCC hydrofined diesel oil distillate oil is treated, and is particularly suitable for deep hydrogenation saturation of the arene of the second section in the two-section hydrogenation modification of diesel oil and then selective ring opening.
CN 102284300A discloses a poor diesel 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, 0.2 to 10 percent of the alkali metal, the alkaline earth metal or the rare earth metal, 5 to 25 percent of WO 3, 8 to 20 percent of MoO 3, 2 to 9 percent of NiO, 1.0 to 5 percent of P and the balance of silicon aluminum oxide carrier in percentage by weight; the catalyst is used for evaluating that raw oil is mixed oil of catalytic cracking and coking diesel, has good reaction activity and stability in condition and stability tests, and can remove more than 90% of sulfur and nitrogen in poor mixed diesel.
CN 102211029A discloses a preparation method of a diesel hydrodesulfurization sulfide catalyst, which comprises the steps of taking metal Ni or Co, mo and Ru as active components, taking Al 2O3 as a carrier, preparing an ethylenediamine solution of ammonium molybdate, adding the carrier for soaking, adding a KBH4 solution of 0.1mol/L, the mol ratio of Mo to B is 1:4, washing the obtained precipitate with water, and drying in a baking oven at 110 ℃ to obtain a catalyst precursor; preparing an ethylenediamine mixed solution of nickel nitrate and ruthenium nitrate, adding a catalyst precursor into the solution for isovolumetric impregnation, naturally airing the obtained precipitate, drying at 120 ℃, roasting at 450 ℃, and vulcanizing at 350 ℃ under the atmosphere of H 2 S to obtain a catalyst; mo is 3-20% according to the weight ratio of the catalyst; ni or Co is 3-10%; ru is 0.1-3%; al 2O3 is the rest; the catalyst has high hydrodesulfurization activity and is used for hydrofining and raw material prerefining hydrodesulfurization.
CN200810113646.5 discloses a diesel hydrofining catalyst, which consists of a carrier and an active component, wherein the active component is one or more of group VIB metal and group VIII metal, and the carrier consists of one or more of SAPO-5, SAPO-11, ZSM-22, ZSM-23 molecular sieves with one-dimensional pore canal and gamma-Al 2O3. The invention further discloses a preparation method of the catalyst on the basis of the diesel hydrofining hydrogenation catalyst. The diesel hydrofining catalyst prepared by the preparation method can effectively realize desulfurization and denitrification of the inferior diesel while preventing the cracking of diesel fractions and realizing the aromatic hydrocarbon hydrogenation saturation of the inferior diesel.
CN200910188174.4 discloses a bulk phase ultra-deep hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises a composite oxide NixWyOz, moO 3, aluminum oxide and a micropore and mesopore composite molecular sieve. 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, pulping with MoO 3, molding and activating. The method not only improves the pore structure of the catalyst, enables more metal active sites to be exposed on the surface of the catalyst and improves the utilization rate of active metals, but also enables the composite molecular sieve to be in uniform and full contact with hydrogenation active metals and to be better matched with the hydrogenation active metals, thereby fully playing the performance of the composite molecular sieve, achieving the effect of ultra-deep desulfurization of diesel, having more obvious effect especially when treating distillate oil with more macromolecule content and being capable of reducing the sulfur content of the diesel to below 10 mug/g.
ZL 201110197778.2 discloses a method for preparing a catalyst carrier with a through large and medium pore, which comprises the following steps: adding solid fiber yarn in the preparation or forming process of the catalyst carrier, dispersing the solid fiber yarn in the catalyst carrier, and then forming and roasting to remove the solid fiber yarn to obtain the catalyst carrier with the through large and medium holes. The invention also provides a method for preparing the catalyst by further carrying the 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 addition of the solid fiber greatly improves the penetration performance of the pore canal in the carrier. The through macropores generated by the fiber filaments provide a rapid diffusion channel for the reaction molecules, thereby reducing mass transfer resistance in the catalytic reaction process. The method is suitable for preparing various catalysts with reaction speed controlled by internal diffusion, such as petroleum fraction (especially heavy oil fraction) hydrogenation catalyst.
MIL-101 (Al) -NH 2 acts as a base catalyst with high reactivity in Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate. The catalyst can be reused without any reduction in activity, and the product can reach high conversion even if it is reacted in a nonpolar solvent. Garibay et Al studied the catalytic effect of the serial cyclic anhydride modification of MIL-53 (Al) -NH 2 on the alcoholysis of certain small molecule epoxy compounds, and compared to find that MIL-53 (Al) -AMMal functionalized with maleic acid serves as the B acid site in the catalyst, promotes the alcoholysis of the epoxy compounds, breaks monopoly of the traditional homogeneous acid catalyst, and the catalyst can be recycled after regeneration, so that 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 uses different preparation methods and modification methods to prepare hydrofining catalyst, and adopts conventional alumina or molecular sieve as carrier, and the modifying agent 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 large specific surface area, proper pore structure, controllable synthesis and functional modification.
Disclosure of Invention
The technical problem to be solved by the invention is a method for improving the activity of a hydrofining catalyst.
In order to solve the problems, the method provided by the invention is mainly based on an aluminum-based MOFs material with large specific surface area, proper pore structure, controllable synthesis and functional modification, and the aluminum-based MOFs material is modified, and the aluminum-based MOFs material is partially modified by mixing the aluminum-based MOFs material with an alumina carrier, so that the effect of improving the pore channel 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.
Since the transition metal contains empty orbitals inside, and is more easily coordinated with organic ligands to form metal-organic framework materials than main group metals, MOFs materials with transition metals as nodes are more diverse in terms of topology and types than main group metal MOFs. Al-MOFs are 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 pore channels, so that the modified MOFs have interaction with guest molecules, and the performance is improved. Under the guidance of controllable design of metal-organic framework materials, the types of Al-MOFs are continuously expanded, functions are continuously improved, applications are also excavated, and a huge family is being formed. Modification of aluminum-based MOFs materials is therefore possible.
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: (1) preparation of modified aluminum-based MOFs materials: uniformly mixing the aluminum-based MOFs material with one or more of titanium oxide, nano silicon dioxide, silica sol, zirconium oxide, boric acid or metatitanic acid, and performing hydrothermal treatment on the mixed mixture to obtain the modified aluminum-based MOFs material. (2) preparation of catalyst support: uniformly mixing pseudo-boehmite powder, a modified aluminum-based MOFs material, a peptizing agent and a forming auxiliary agent, adding deionized water and nitric acid, kneading into a plastic body soft block in a kneader, putting the plastic body soft block into a trough of a strip extruder, extruding strips and granulating through a clover-shaped pore plate, and then carrying out health maintenance, drying and roasting to obtain a clover-shaped carrier; (3) preparation of impregnating solution: 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 the active component metal salt, and continuously adding deionized water to the volume of the prepared solution to obtain an active component co-impregnation liquid; (4) preparation of a catalyst: placing the clover-shaped alumina carrier prepared in the step (2) into an impregnating tank, adding the impregnating liquid prepared in the step (3) to obtain a catalyst wet strip, and carrying out health maintenance, drying and roasting to obtain the clover-shaped hydrofining catalyst.
Preparation of modified aluminum-based MOFs materials: preferred aluminum-based MOFs materials are any one or a combination of several of MIL-53 (AI), MIL-96 (AI), MIL-100 (AI), or MIL-110 (AI); the modifier is one or a combination of more of titanium oxide, nano silicon dioxide, 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, a step of; the preferred conditions for the hydrothermal treatment are: 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 that the temperature is 500-600 ℃, and the treatment time is 2-6 hours.
Preparation of the catalyst support: 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 additive 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 more of citric acid, tartaric acid, oxalic acid, ethylenediamine tetraacetic acid and the like; the molding auxiliary agent is one or more of sesbania powder, methyl cellulose, carbon black and the like; the conditions of curing, drying and roasting of the molded carrier are as follows: preserving the health for 2-4 h at room temperature, drying for 2-6 h at 100-150 ℃, and roasting for 4-8 h at 400-600 ℃.
Preparation of the catalyst: the catalyst curing, drying and roasting conditions in the step (4) are as follows: preserving the health for 2-10 h at room temperature, drying for 2-6 h at 100-150 ℃, and roasting for 2-10 h at 400-600 ℃.
The invention also provides a hydrofining catalyst based on the modified aluminum-based MOFs material, which is prepared by the preparation method, wherein the content of active components is 0-10wt% of cobalt oxide, 5-20wt% of molybdenum oxide, 0-10wt% of nickel oxide, 10-25wt% of tungsten oxide, 0-10wt% of phosphorus pentoxide, 5-20wt% of titanium dioxide and 5-20wt% of silicon dioxide, and the total weight of the hydrofining catalyst is taken as a reference.
The hydrofining catalyst is suitable for the petroleum fraction hydrotreatment with the distillation range of 40-390 ℃, adopts a single-stage single-agent process flow, has the reaction temperature of 240-390 ℃ under the condition of the existence of hydrogen after the catalyst is vulcanized, has the hydrogen partial pressure of 0.5-12.0 MPa, has the hydrogen-oil volume ratio of 80-500:1, and has the liquid hourly space velocity of 1.0-8.0 h -1.
Compared with the prior art, the hydrofining catalyst of the modified aluminum-based MOFs material and the preparation method thereof are developed, the catalyst adopts the modification treatment of the aluminum-based MOFs material, the modification treatment mode is simple and practical, the modified aluminum-based MOFs material and the conventional alumina material are mixed to obtain the catalyst carrier with improved pore structure and surface property, the pore channel 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 high activity, stable catalyst performance and strong coking resistance in the hydrogenation reaction process, and has the characteristic of wide raw material treatment. The method has the advantages of simplicity, easy implementation, obvious effect after implementation and the like.
Detailed Description
The invention provides a hydrofining catalyst based on a modified aluminum-based MOFs material and a preparation method thereof. For further illustration of the invention, the following examples are given, but are not intended to limit the scope of the invention as defined in the appended claims.
Example 1:
100g of aluminum-based MOFs material MIL-53 (AI), 3g of titanium dioxide, 1g of meta-titanic acid and 2g of phosphoric acid are fully and uniformly mixed, and then are put into a hydrothermal device for hydrothermal treatment, and water vapor is introduced under the conditions that the set pressure is 0.3MPa and the temperature is 450 ℃ for 3 hours. The treated mixed sample was calcined in a muffle furnace at 500℃for 2 hours to obtain a modified aluminum-based MOFs material, which was designated as 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 silicon dioxide, 17g of silica sol (the silicon dioxide content is 30 wt%) and 5g of phosphoric acid are fully and uniformly mixed, and then the mixture is put into a hydrothermal device for hydrothermal treatment, and steam is introduced under the conditions that the set pressure is 0.4MPa and the temperature is 750 ℃ for 8 hours. The treated mixed sample was calcined in a muffle furnace at 600℃for 6 hours to obtain a modified aluminum-based MOFs material, which was designated as 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, and steam is introduced under the condition that the set pressure is 0.35MPa and the temperature is 550 ℃ for 5 hours. The treated mixed sample was calcined in a muffle furnace at 550℃for 4 hours to obtain a modified aluminum-based MOFs material, which was designated as sample 3.
Example 4:
Mixing 100g of commercial pseudo-boehmite, 1g of sample 1, 5g of field-drum powder mechanically for 30min; 3g of citric acid is dissolved in 80g of deionized water, 15g of 68% nitric acid is added into the evenly mixed powder, and wet mixing is carried out for 35min, thus obtaining the plastic soft block. Adding the obtained plastic soft block into a trough of a strip extruder, extruding with a clover-shaped pore plate, and granulating to obtain the clover-shaped carrier. Then preserving the mixture at room temperature for 2 hours, drying the mixture for 4 hours at 120 ℃ in air atmosphere, putting the mixture into a muffle furnace for roasting for 4 hours at 450-550 ℃ in air atmosphere, and obtaining the hydrofining catalyst carrier 1.
Example 5:
100g of commercial pseudo-boehmite, 15g of sample 2, tianfen g of methyl cellulose and 2g of methyl cellulose are mechanically mixed for 30min; 2g of citric acid and 2g of tartaric acid are dissolved in 80g of deionized water, 15g of nitric acid with the concentration of 68% is added into the evenly mixed powder, and wet mixing is carried out for 35min, thus obtaining the plastic soft block. Adding the obtained plastic soft block into a trough of a strip extruder, extruding with a clover-shaped pore plate, and granulating to obtain the clover-shaped carrier. And then preserving the mixture at room temperature for 2 hours, drying the mixture for 4 hours at 120 ℃ in an air atmosphere, putting the mixture into a muffle furnace for roasting for 4 hours at 450-550 ℃ in the air atmosphere, and obtaining the hydrofined catalyst carrier 2.
Example 6:
100g of commercial pseudo-boehmite, 10g of sample 3, 2g of field-drum powder and 3g of carbon black are mechanically mixed for 30min; 1g of citric acid and 2g of oxalic acid are dissolved in 80g of deionized water, 15g of nitric acid with the concentration of 68% is added into the evenly mixed powder, and wet mixing is carried out for 35min, thus obtaining the plastic soft block. Adding the obtained plastic soft block into a trough of a strip extruder, extruding with a clover-shaped pore plate, and granulating to obtain the clover-shaped carrier. Then preserving the mixture at room temperature for 2 hours, drying the mixture for 4 hours at 120 ℃ in air atmosphere, putting the mixture into a muffle furnace for roasting for 4 hours at 450-550 ℃ in air atmosphere, and obtaining the hydrofining catalyst carrier 3.
Example 7:
Adding 35g of phosphoric acid into 300g of deionized water, stirring uniformly, adding 85g of industrial molybdenum trioxide, 165g of industrial ammonium metatungstate and 210g of industrial nickel nitrate into a phosphoric acid solution, stirring continuously, 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 the impregnating solution 1.
Example 8:
adding 50g of phosphoric acid into 300g of deionized water, stirring uniformly, adding 50g of industrial molybdenum trioxide, 105g of industrial ammonium metatungstate and 60g of industrial basic nickel carbonate into a phosphoric acid solution, stirring continuously, 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 an impregnating solution 2.
Example 9:
And (3) respectively taking 100g of the prepared hydrofining catalyst carriers 1,2 and 3, placing into an impregnation tank, adding the impregnation liquid 1, adopting equal volume impregnation for 40min, then carrying out health maintenance at room temperature for 2h, drying at 120 ℃ for 4h, placing into a muffle furnace for roasting at 500 ℃ for 4h in an air atmosphere, and thus obtaining 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 into an impregnation tank, adding an impregnation liquid 2, adopting equal volume impregnation, carrying out impregnation for 40min, then carrying out health maintenance at room temperature for 2h, drying at 120 ℃ for 4h, placing into a muffle furnace for roasting at 500 ℃ for 4h in an air atmosphere, and thus obtaining hydrofining catalysts 4, 5 and 6.
Example 11
Comparative hydrogenation evaluations were performed on hydrofinishing catalysts 1,2, 3, 4, 5, 6 and comparative samples, which were conventional hydrofinishing catalysts without the addition of modified aluminum-based MOFs materials.
The apparatus used was a 200mL small hydrogenation apparatus. The reactor was charged with 200mL of catalyst and gradually warmed to 370deg.C under hydrogen atmosphere, and the catalyst was presulfided with kerosene containing 2.0% CS 2 for 40h. The mass ratio of the raw oil to the catalytic diesel is 1:1, wherein the sulfur content is 7000 mug/g, and the nitrogen content is 760 mug/g. The reaction conditions are as follows: pressure 6.4MPa, temperature: 360 ℃, airspeed: 2.0h -1, hydrogen oil volume ratio: 400:1. the comparative evaluation results are shown in Table 1.
Table 1 comparison of the performance of catalysts in hydrodesulfurization reactions
The activity is expressed as relative activity, i.e. the activity of the corresponding untreated catalyst for 200 hours is 100, and the activity obtained by comparing the activity of the catalyst according to the invention with that of the catalyst according to the invention is expressed as relative activity. The relative desulfurization activity was calculated according to the following formula:
relative desulfurization Activity=100× [ (1/Sp) 0.65-(1/Sf)0.65]/[(1/Spr)0.65-(1/Sfr)0.65 ]
Wherein Sfr and Spr respectively represent the sulfur-containing concentration of the diesel fraction used by the reference agent and the product after the hydrogenation treatment of the reference agent, and Sf and Sp respectively represent the sulfur-containing concentration of the diesel fraction used by the catalyst and the product after the hydrogenation treatment of the catalyst.
Claims (5)
1. A method for preparing a hydrofining catalyst based on modified aluminum-based MOFs materials, which is characterized by comprising the following steps:
(1) Preparation of modified aluminum-based MOFs materials: uniformly mixing an aluminum-based MOFs material with a modifier to obtain a mixture, performing hydrothermal treatment on the mixture, and roasting to obtain a modified aluminum-based MOFs material;
(2) Preparation of the catalyst support: uniformly mixing pseudo-boehmite powder, a modified aluminum-based MOFs material, a peptizing agent and a forming auxiliary agent, adding deionized water and nitric acid, kneading, extruding strips, granulating, and then carrying out health maintenance, drying and roasting to obtain a catalyst carrier;
(3) Preparing an impregnating solution: adding the 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 a co-impregnating solution of the active component;
(4) Preparation of the catalyst: placing the catalyst carrier prepared in the step (2) into an impregnation tank, adding the co-impregnation liquid of the active components prepared in the step (3), and carrying out health maintenance, drying and roasting to obtain the hydrofining catalyst based on the modified aluminum-based MOFs material;
In the step (1), the hydrothermal treatment condition is that 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 that the temperature is 500-600 ℃, and the roasting time is 2-6 hours;
the modifier is at least one selected from titanium oxide, nano silicon dioxide, silica sol, zirconium oxide, boric acid and metatitanic acid;
the peptizing agent is one or more of citric acid, tartaric acid, oxalic acid and ethylenediamine tetraacetic acid;
the forming auxiliary agent is one or more of sesbania powder, methyl cellulose and carbon black;
based on the total weight of the hydrofining catalyst, the hydrofining catalyst contains 0-10wt% of cobalt oxide, 5-20wt% of molybdenum oxide, 0-10wt% of nickel oxide, 10-25wt% of tungsten oxide, 5-20wt% of titanium dioxide and 5-20wt% of silicon dioxide.
2. The preparation method of claim 1, wherein in the step (2), the curing condition is curing for 2-4 hours at room temperature; the drying temperature is 100-150 ℃, and the drying time is 2-6 hours; the roasting temperature is 400-600 ℃, and the roasting time is 4-8 hours.
3. The preparation method of claim 1, wherein in the step (4), the curing condition is curing for 2-10 hours at room temperature; the drying time is 100-150 ℃ and 2-6 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
4. The preparation method according to claim 1, wherein in the step (2), the plastic body soft blocks are kneaded in a kneader, the plastic body soft blocks are put into a trough of a strip extruder, extruded by a clover-shaped pore plate, pelletized, and then subjected to health maintenance, drying and roasting to obtain the clover-shaped catalyst carrier; in the step (4), the hydrofining catalyst based on the modified aluminum-based MOFs material is clover-shaped.
5. The application of the hydrofining catalyst obtained by the preparation method according to any one of claims 1-4 in hydrogenation reaction, which is characterized in that the hydrofining catalyst is suitable for hydrotreating petroleum fractions with a distillation range of 40-390 ℃, a single-stage single-agent process flow is adopted, the hydrofining catalyst is vulcanized and then reacts in the presence of hydrogen at a reaction temperature of 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 space velocity is 1.0-8.0 h -1.
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