CN115245830A - Inferior residual oil hydrodemetallization catalyst and preparation method thereof - Google Patents
Inferior residual oil hydrodemetallization catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN115245830A CN115245830A CN202110459132.0A CN202110459132A CN115245830A CN 115245830 A CN115245830 A CN 115245830A CN 202110459132 A CN202110459132 A CN 202110459132A CN 115245830 A CN115245830 A CN 115245830A
- Authority
- CN
- China
- Prior art keywords
- pore
- poor
- catalyst
- hydrodemetallization catalyst
- residual oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 55
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QZNWNKFWDJRMLV-UHFFFAOYSA-N azane;2-hydroxy-4-[(4-hydroxy-1,3,2,4-dioxadiboretan-2-yl)oxy]-1,3,2,4-dioxadiboretane;tetrahydrate Chemical compound N.N.O.O.O.O.O1B(O)OB1OB1OB(O)O1 QZNWNKFWDJRMLV-UHFFFAOYSA-N 0.000 claims description 4
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- AETFVXHERMOZAM-UHFFFAOYSA-N B(O)(O)O.N.N Chemical compound B(O)(O)O.N.N AETFVXHERMOZAM-UHFFFAOYSA-N 0.000 claims description 3
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- 230000032683 aging Effects 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- UFMBFIIJKCBBHN-MEKJRKEKSA-N myelin peptide amide-16 Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(N)=O)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CO)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](C)NC(=O)[C@H](C)NC(C)=O)C1=CC=C(O)C=C1 UFMBFIIJKCBBHN-MEKJRKEKSA-N 0.000 description 1
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
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- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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Classifications
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- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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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
- 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
- B01J35/615—100-500 m2/g
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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
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- B01J35/63—Pore volume
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
- C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention relates to a poor residual oil hydrodemetallization catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-enlarging agent, then adding an aqueous solution containing a chemical pore-enlarging agent, ammonia and low carbon alcohol, kneading, molding, drying and roasting, and then loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-enlarging agent is water-soluble organic polymer, and the chemical pore-enlarging agent is boron-containing compound. The catalyst prepared by the method has a bimodal pore structure and a large pore volume and a large pore diameter, has high demetallization activity and strong metal capacity, and is particularly suitable for hydrotreating inferior heavy oil and residual oil.
Description
Technical Field
The invention relates to a poor-quality residual oil hydrodemetallization catalyst and a preparation method thereof, in particular to a high-activity high-impurity-capacity catalyst for poor-quality heavy oil hydrodemetallization treatment and a preparation method thereof.
Background
Currently, with the increasing deterioration and deterioration of petroleum resources worldwide, and the urgent requirement for upgrading oil quality and the increasing strictness of environmental regulations, there is an urgent need to develop clean and efficient heavy oil processing technologies. Hydrogenation is the most effective heavy oil and residual oil raw material processing technology. Through hydrogenation, remove most metallic impurity and sulphur, reduce the carbon residue value simultaneously, improve the quality of heavy oil, provide the possibility for its further high-efficient clean processing. The combination of heavy oil and residual oil hydrotreating and heavy oil catalytic cracking technology can convert residual oil which has low utilization value and easily causes environmental pollution to the maximum extent, and greatly improve the yield of light oil; and clean oil products with high added value and superior quality can be obtained. In a certain sense, the crude oil is converted by 100 percent, and the desire of completely drying and squeezing the crude oil in the petroleum refining process is realized. The technology combination becomes a core technology for improving economic benefits of sulfur-containing crude oil processing and refining enterprises.
The heavy oil is permanently poisoned by the deposition of metals such as Na, ca, ni, V and the like on the hydrogenation catalyst, and is an important factor to be considered in the hydrogenation process of the heavy oil. The Hydrodemetallization (HDM) catalyst is one of key technologies in the heavy oil hydrotreating process, and mainly has the functions of removing most of Ni, V and other metal impurities in raw materials, protecting downstream desulfurization (HDS) and denitrification (HDN) catalysts and simultaneously having certain desulfurization capacity. Such catalysts need to have not only good metal removal capacity, but also high metal impurity holding capacity. As most metal impurities in the residual oil exist in colloid and asphaltene, which are the types with the largest molecular weight, the most complex structure and the strongest polarity in the petroleum components, the diffusion resistance is larger. The demetallization agent is restricted by the mass transfer and diffusion efficiency of the carrier, the orifice is easy to block, the deposition distribution of the removed impurities is seriously uneven, and the metal-containing capacity is limited. All the above causes serious waste of the internal space of the catalyst, and the efficiency of the catalyst cannot be brought into full play. Therefore, the catalyst has larger pore volume, pore diameter and good pore permeability, so as to be beneficial to the diffusion and reaction of macromolecular substances such as asphaltene containing metal impurities in residual oil raw materials and the deposition of the metal impurities. One of the solving approaches is to adopt a carrier with a bimodal pore structure, and in the reaction process, macropores with the pore diameter of more than 100nm provide channels for the diffusion of macromolecular reaction substances, so that impurities are promoted to diffuse and deposit to the inner pore channels of the catalyst; and the pore channels with the pore diameter of less than 50nm provide reaction surfaces and deposition sites for impurities. The two kinds of pore canals act synergistically, so that the catalyst has high demetallization activity and high impurity capacity.
CN1103009A discloses a process for preparing alumina carrier with double pores, which comprises mixing two aluminas or their precursors with different pore size distributions, carbon black powder, surfactant, peptizing agent and water, drying and calcining. When the carbon black powder is used as a pore-enlarging agent, the pore-enlarging effect is poor, the strength of the carrier is low, and meanwhile, the pore volume and the pore diameter of the carrier can be reduced by adding the peptizing agent.
CN1120971 discloses a method for preparing an alumina carrier with a bimodal pore structure, which uniformly mixes two or more than two pseudo-boehmite dry gels prepared by different raw material route methods, and then carries out peptization, molding, drying and roasting. However, the method adopts the oil ammonia column method to mold the alumina carrier, has low production efficiency and large pollution in the production process, and is less adopted at present.
CN1647857A discloses a preparation method of a macroporous alumina carrier, which comprises the steps of forming and roasting a pseudo-thin diasphore composition containing an organic pore-expanding agent to obtain the alumina carrier with a bimodal pore structure. The method needs to pulp the organic pore-expanding agent and the pseudo-boehmite and spray-dry the pulp, and the preparation process is complex.
CN105983443B discloses a preparation method of a bimodal pore structure alumina carrier, which comprises the steps of mixing, molding and roasting an organic binder, a chemical pore-enlarging agent and a physical pore-enlarging agent to obtain a large-pore-volume bimodal pore structure alumina carrier. The pore diameter of the carrier prepared by the method is increased limitedly, the proportion of macropores is greatly influenced by the addition amount of the pore-expanding agent, the carrier with larger pore diameter and proportion of macropores cannot be prepared, the roasting temperature of the carrier is higher, and the production cost is high.
In the existing preparation technology of alumina carrier and catalyst, acid substances such as nitric acid, acetic acid, aluminum nitrate and the like are mostly needed to be added as peptizing agents when alumina is formed, and the addition of the acid substances can destroy the particle structure of the alumina and reduce the pore volume and the pore diameter of the carrier. The organic binder is used for replacing peptized acid to carry out carrier molding, so that the pore volume and the pore diameter of the carrier can be increased to a certain extent, but the effect is limited. The existing method only increases the pore-expanding agent when increasing the macroporous proportion of the carrier, and has the problems of increased cost, difficult molding, reduced strength and the like when preparing the carrier and the catalyst with the high macroporous proportion and the bimodal porous structure.
Disclosure of Invention
The invention aims to provide a preparation method of a residual oil hydrodemetallization catalyst with a bimodal pore structure, large pore volume and large pore diameter and low cost aiming at the defects of the prior art.
In order to achieve the aim, the invention provides a preparation method of a poor-quality residual oil hydrodemetallization catalyst, which comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-enlarging agent, then adding an aqueous solution containing a chemical pore-enlarging agent, ammonia and low carbon alcohol, kneading, molding, drying and roasting, and then loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-enlarging agent is water-soluble organic polymer, and the chemical pore-enlarging agent is boron-containing compound.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more water-soluble organic polymers from polyethylene glycol, polyacrylamide, polyvinyl alcohol and crospovidone, wherein the addition amount of the water-soluble organic polymers is 1-6% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more boron-containing compounds from boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, wherein the adding amount of the boron-containing compounds is 0.3-2% of the weight of alumina in terms of elemental boron.
The preparation method of the inferior residual oil hydrodemetallization catalyst, disclosed by the invention, has the advantage that the adding amount of ammonia is 0.05-0.5% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more of methanol, ethanol, glycol, propanol, isopropanol and glycerol as low-carbon alcohols, wherein the addition amount of the low-carbon alcohols is 0.5-5% of the weight of alumina
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the following steps that the active metal comprises a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst calculated by oxides, and the cobalt and/or nickel accounts for 0.4-2%.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, wherein the addition amount of the synthetic cellulose is 1-5% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst is characterized in that the viscosity of a 2% aqueous solution of the synthetic cellulose is not lower than 50000mPa & s.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, is characterized in that the particle size of the water-soluble organic polymer is 80-400 meshes.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst is characterized in that the forming process is carried out by adopting an oil pressure or hydraulic strip extruding machine, and the extrusion pressure is 10-30 MPa.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, has the advantages that the roasting temperature is 500-1100 ℃, and the roasting time is 0.5-4 hours.
In order to realize the purpose, the invention also provides a poor-quality residual oil hydrodemetallization catalyst prepared by the method.
Compared with the prior art, the method provided by the invention does not use an acidic peptizing agent in the carrier forming process, thereby reducing the damage of acid to the hydrated alumina particle structure; a small amount of ammonia is added, on one hand, the ammonia can effectively promote the composite pore-expanding effect of the chemical pore-expanding agent and the organic pore-expanding agent, for example, the ammonia can promote the 'gelation' reaction between boric acid and polyvinyl alcohol, the proportion of macropores with the size of more than 100nm in the carrier is effectively improved, on the other hand, the ammonia can effectively reduce the bonding strength among alumina particles, and the pore volume and the pore diameter of the carrier are increased; the low-carbon alcohol component is added, the solubility of the low-carbon alcohol to boric acid or a boron-containing compound and the affinity between the low-carbon alcohol and the organic pore-expanding agent are utilized, the interaction between the boron-containing chemical pore-expanding agent and the organic pore-expanding agent is promoted, and the boron-containing compound component is reduced from entering the inside of an alumina pore channel, so that more macroporous structures are generated, and the pore-expanding efficiency is improved; the addition amount of the organic pore-expanding agent is low, and the preparation cost is reduced.
The invention has the beneficial effects that:
the catalyst prepared by the method has a bimodal pore structure, and has a large pore volume and a large pore diameter, and the prepared catalyst has high demetallization activity and strong metal capacity, and is particularly suitable for hydrotreating inferior heavy oil and residual oil. For example, the catalyst prepared by the method provided by the invention has the specific surface area of 133 square meters per gram and the pore volume of 1.21 ml/g, and has characteristic peaks at 21 nm and 470 nm respectively, wherein the pores with the pore diameter of 20-50 nm account for 38.9 percent of the total pore volume, the pores with the pore diameter of more than 100nm account for 39.5 percent of the total pore volume, the pores with the pore diameter of less than 20nm account for 21.6 percent of the total pore volume, and the catalyst contains 4.3 percent of molybdenum oxide and 1.3 percent of nickel oxide; the poor middle east residual oil with the metal (Ni + V) content of 103 mu g/g is used as a raw material, and the demetallization rate reaches 81.3 percent in 200 hours, 71.0 percent in 2000 hours and 65.8 percent in 4000 hours under the conditions of 16MPa of reaction pressure, 380 ℃ of reaction temperature and 1.0h < -1 > of airspeed.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
A preparation method of a poor-quality residual oil hydrodemetallization catalyst comprises the following steps: mixing hydrated alumina with a powdery adhesive and an organic pore-enlarging agent, then adding an aqueous solution containing a chemical pore-enlarging agent, ammonia and low-carbon alcohol, kneading, molding, drying and roasting to obtain a carrier, and then loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-enlarging agent is a water-soluble organic polymer, and the chemical pore-enlarging agent is a boron-containing compound.
The shape of the carrier can be changed according to the needs, such as a cylinder, clover, butterfly, five-tooth ball and the like. During the forming process, a proper amount of extrusion aid (such as sesbania powder) and water can be added.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of preparing a mixture of one or more of gibbsite, boehmite, pseudoboehmite and amorphous aluminum hydroxide from hydrated alumina. Preferably pseudoboehmite. They may be commercially available or prepared by any method known in the art. For example, the aluminum sulfate-sodium metaaluminate method is adopted to prepare the pseudo-boehmite.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more water-soluble organic polymers from polyethylene glycol, polyacrylamide, polyvinyl alcohol and crospovidone, wherein the addition amount of the water-soluble organic polymers is 1-6% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more boron-containing compounds from boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, wherein the adding amount of the boron-containing compounds is 0.3-2% of the weight of alumina in terms of elemental boron.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, comprises the step of adding ammonia in an amount of 0.05-0.5% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more of methanol, ethanol, glycol, propanol, isopropanol and glycerol from low-carbon alcohols, wherein the addition amount of the low-carbon alcohol is 0.5-5% of the weight of alumina
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the following step of preparing a catalyst, wherein the active metal comprises a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst, and the cobalt and/or nickel accounts for 0.4-2% of the total weight of the catalyst.
The active metal is loaded by a dipping mode, and the active metal can be prepared into a stable metal solution by any known method, for example, the stable metal solution can be prepared by adding ammonia water with a certain concentration into ammonium heptamolybdate and nickel nitrate under the stirring condition for dissolving or dissolving molybdenum trioxide, basic nickel carbonate and phosphoric acid together under the heating and stirring conditions.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst comprises the step of selecting one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, wherein the addition amount of the synthetic cellulose is 1-5% of the weight of alumina.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, is characterized in that the viscosity of a 2% aqueous solution of the synthetic cellulose is not lower than 50000mPa & s.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, is characterized in that the particle size of the water-soluble organic polymer is 80-400 meshes.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst is characterized in that the forming process is carried out by adopting an oil pressure or hydraulic strip extruding machine, and the extrusion pressure is 10-30 MPa.
The preparation method of the poor-quality residual oil hydrodemetallization catalyst, disclosed by the invention, has the advantages that the roasting temperature is 500-1100 ℃, and the roasting time is 0.5-4 hours.
The poor-quality residual oil hydrodemetallization catalyst prepared by the method.
The catalyst provided by the method has large pore volume and pore diameter and a bimodal pore structure, and if the catalyst is measured by a mercury intrusion method, the pore volume is 0.8-1.6 ml/g, pores with the pore diameter of 20-50 nanometers account for 30-70% of the total pore volume, pores with the pore diameter of more than 100 nanometers account for 20-50% of the total pore volume, the proportion of pores with the pore diameter of less than 20 nanometers to the total pore volume is less than 30%, and the BET specific surface area is 80-220 square meters/g.
The catalyst provided by the method has large pore volume and pore diameter and a bimodal pore structure, and can be used as an inferior residual oil hydrotreating catalyst, in particular a residual oil hydrodemetallization catalyst.
The following examples and comparative examples are used to further illustrate the features of the present invention.
Example 1
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content is 71.5 wt%) produced by Nicotiana constant-luminance chemical company Limited, adding 10.7g of hydroxypropyl methyl cellulose with viscosity of 15 ten thousand mPa.s (viscosity of 2% aqueous solution) and 14.3g of polyvinyl alcohol powder with particle size of 120 meshes, and uniformly mixing; 14.3g of boric acid was dissolved in 607.8g of purified water, and 5g of concentrate was addedUniformly stirring ammonia water with the concentration of 20% and 10g of ethanol, slowly adding the mixture into the materials, kneading the materials into a plastic body, and extruding the plastic body into a clover shape with the diameter of 1.6mm on an oil pressure type extruder, wherein the extrusion pressure is controlled to be 20MPa. Drying at 120 deg.C for 2.0 hr, placing into high-temperature roaster, and maintaining at 900 deg.C for 3 hr to obtain the carrier. The formulation contained (3.8 g of MoO) 3 +0.8g of NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst A. The catalyst physical properties are shown in Table 1.
Example 2
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content 71.5 wt%) produced by Nicoti Henghui chemical company, adding 3.6g of hydroxypropyl methyl cellulose with viscosity of 20 ten thousand mPa.s (viscosity of 2% aqueous solution), 11.5g of polyvinyl alcohol powder with granularity of 80 meshes and 10.0g of polyethylene glycol powder with granularity of 120 meshes, and uniformly mixing; dissolving 20.4g of ammonium tetraborate tetrahydrate in 607.8g of purified water, adding 0.89g of ammonia water with the concentration of 20%, 10g of ethylene glycol and 7.88g of methanol, stirring uniformly, slowly adding the mixture into the above materials, kneading into a plastic body, extruding into a clover shape with the diameter of 1.6mm on an oil pressure type extruding machine, and controlling the extrusion pressure to be 10MPa. Then placing the mixture into a high-temperature roasting furnace, and keeping the temperature of 1100 ℃ for 0.5 hour to obtain the carrier. The formulation contained (1.4 g MoO) 3 +1.4g Co 2 O 3 ) 100mL of stable metal impregnation liquid, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst B. The catalyst physical properties are shown in Table 1.
Example 3
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content 71.5 wt%) produced by Nicoti Henghui chemical company Limited, adding 17.9g of hydroxyethyl methyl cellulose with viscosity of 10 ten thousand mPa.s (viscosity of 2% aqueous solution) and 17.9g of polyacrylamide with particle size of 200 meshes, and uniformly mixing; dissolving ammonium borate 5.67g in water 607.8g, adding ammonia water with concentration of 20% 8.94g and propanol 1.79g, stirring, slowly adding into the above materials, kneading into plastic, and making into oil pressure typeExtruding the mixture on a strip extruder to form a clover shape with the diameter of 1.6mm, and controlling the extrusion pressure to be 30MPa. Then placing the mixture into a high-temperature roasting furnace, and keeping the temperature of 500 ℃ for 4 hours to obtain the carrier. The formulation contained (5.5 g WO) 3 +1.8g MoO 3 +0.9g NiO+0.5g Co 2 O 3 ) 100mL of stable metal impregnation liquid, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst C. The catalyst properties are shown in Table 1.
Example 4
Weighing 500g of the pseudo-boehmite, adding 6.7g of hydroxypropyl methylcellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2 percent of water solution) and 4.0g of methylcellulose with the viscosity of 10 ten thousand mPa.s (the viscosity of 2 percent of water solution) and 3.6g of crospovidone with the granularity of 160 meshes, and uniformly mixing; dissolving 29.0g of metaboric acid in 607.8g of purified water, adding 7.5g of ammonia water with the concentration of 20% and 8g of isopropanol, uniformly stirring, slowly adding the above materials, kneading into a plastic body, and extruding into clover shape with the diameter of 1.6mm on an oil pressure type extruding machine, wherein the extrusion pressure is controlled to be 18MPa. Then placing the mixture into a high-temperature roasting furnace, and keeping the temperature at 800 ℃ for 3 hours to obtain the carrier. The formulation contained (3.3 g MoO) 3 +1.2g NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; and drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst D. The catalyst properties are shown in Table 1.
Example 5
Weighing 500g of the pseudo-boehmite, adding 10.7g of ethyl cellulose with the viscosity of 15 ten thousand mPa.s (the viscosity of 2 percent aqueous solution), 5.7g of polyvinyl alcohol powder with the granularity of 400 meshes and 5.0g of polyacrylamide with the granularity of 80 meshes, and uniformly mixing; dissolving 20.4g of boric acid and 4.7g of ammonium pentaborate tetrahydrate in 607.8g of purified water, adding 6g of ammonia water with the concentration of 20% and 15g of glycerol, uniformly stirring, slowly adding the mixture into the materials, kneading the materials into a plastic body, and extruding the plastic body into a clover shape with the diameter of 1.6mm on an oil pressure type extruding machine, wherein the extrusion pressure is controlled to be 20MPa. Then placing the mixture into a high-temperature roasting furnace, and keeping the temperature of 950 ℃ for 2.5 hours to obtain the carrier. The formulation contained (4.7 g MoO) 3 +0.3g NiO)/100 mL of stable Metal impregnationImpregnating the obtained carrier by a saturated impregnation method; and drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain a catalyst E. The catalyst properties are shown in Table 1.
Comparative examples 1-3 illustrate the prior art process and bimodal pore structure alumina supports prepared by the prior art process.
Comparative example 1
The comparative example was prepared according to the method described in CN 1103009A.
Mixing 34.1g of aluminum hydroxide dry glue powder (containing 75% of aluminum oxide of alkyl aluminum hydrolysate) and 39.3g of aluminum hydroxide powder prepared by an aluminum sulfate method, adding 4.7g of high-wear-resistance carbon black, 3.5g of surfactant SA-20, 2.1g of aluminum nitrate and 66 ml of water, fully grinding and mixing, extruding into clover shapes with the diameter of 1.8 mm on an extruder, drying at 120 ℃, and roasting at 600 ℃ for 4 hours to obtain the carrier. The formulation contained (14.0 g MoO) 3 +2.9g NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; and drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst F. The catalyst physical properties are shown in Table 1.
Comparative example 2
In this comparative example, alumina carrier and catalyst were prepared as described in CN 1647857A.
NaAlO with the concentration of 200g aluminum oxide/liter is prepared by the reaction of aluminum hydroxide and aluminum hydroxide 2 Adding the solution and aluminum sulfate solution with the concentration of 90g of alumina/liter into a 2-liter gelatinizing tank simultaneously in a parallel flow mode, wherein 1.5 liters of water is placed into the tank in advance, the flow rate of sodium metaaluminate is 1.1 liter/hour, the flow rate of the aluminum sulfate solution is adjusted to ensure that the pH value of gelatinizing is 8, the gelatinizing temperature is 50 ℃, and slurry generated by gelatinizing is collected in an aging tank. And adding sodium carbonate into the collected aging tank to adjust the pH value to 10, aging for 50 minutes, filtering and washing to obtain the pseudo-boehmite wet filter cake. Mixing 6.5 kg of the wet filter cake with 20.5g of sesbania powder, adding the mixture into the mixture for pulping, then carrying out spray drying at the inlet temperature of 600 ℃ and the outlet temperature of 145 ℃, extruding the dried composition on a strip extruding machine for forming strips, drying at 120 ℃, roasting at 800 ℃ for 3 DEG CAnd 5 hours, obtaining the carrier. The formulation contained (10.0 g MoO) 3 +1.3g NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; and drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst G. The catalyst physical properties are shown in Table 1.
Comparative example 3
The comparative example was prepared according to the method described in CN105983443B for alumina support and catalyst.
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content 71.5 wt%) produced by Nicoti Henghui chemical company Limited, adding 10.7g of hydroxypropyl methyl cellulose with viscosity of 15 ten thousand mPa.s (viscosity of 2% aqueous solution) and 17.9g of polyvinyl alcohol powder with particle diameter of 90-150 mu m, and uniformly mixing; dissolving 14.3g of boric acid in 390g of purified water, slowly adding the boric acid into the materials, kneading the materials into a plastic body, and extruding the plastic body into a clover shape with the diameter of 1.6mm on a front extrusion type single-screw extruder. Drying at 120 deg.C for 2.0 hr, placing in a roaster, and keeping at 800 deg.C for 3 hr to obtain the carrier. The formulation contained (5.0 g of MoO) 3 +1.1 gNiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; and drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst H. The catalyst physical properties are shown in Table 1.
Comparative example 4
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content 71.5 wt%) produced by Nicoti Henghui chemical company Limited, adding 10.7g of hydroxypropyl methyl cellulose with viscosity of 15 ten thousand mPa.s (viscosity of 2% aqueous solution), and mixing uniformly; 58.8g of boric acid is dissolved in 390g of purified water, slowly added into the materials, kneaded into a plastic body, and extruded into a clover shape with the diameter of 1.6mm on a front extrusion type single-screw extruder. Drying at 120 deg.C for 2.0 hr, placing in a roaster, and keeping at 800 deg.C for 3 hr to obtain the carrier. The formulation contained (8.1 g MoO) 3 +1.7g NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; drying the impregnated material at 120 ℃, and keeping the temperature of 500 ℃ in a roasting furnace for 3 hours to obtain the catalyst I. The catalyst physical properties are shown in Table 1.
Comparative example 5
Weighing 500g of macroporous pseudoboehmite dry glue powder (dry basis content 71.5 wt%) produced by Nicoti Henghui chemical company Limited, adding 10.7g of hydroxypropyl methyl cellulose with viscosity of 15 ten thousand mPa.s (viscosity of 2% aqueous solution) and 58.8g of polyvinyl alcohol powder with particle diameter of 90-150 mu m, and uniformly mixing; 390g of purified water is slowly added into the materials, kneaded into plastic bodies, and then extruded into clover shapes with the diameter of 1.6mm on a front extrusion type single-screw extruder. Drying at 120 deg.C for 2.0 hr, placing in a roaster, and holding at 800 deg.C for 3 hr to obtain the carrier. The formulation contained (7.2 g MoO) 3 +1.5g NiO)/100 mL of stable metal impregnation solution, and impregnating the obtained carrier by a saturated impregnation method; the impregnated material is dried at 120 ℃, and is kept at the constant temperature of 500 ℃ for 3 hours in a roasting furnace to obtain the catalyst J. The catalyst physical properties are shown in Table 1.
TABLE 1 physicochemical Properties of the catalyst
The results in table 1 show that, compared with the comparative example, the catalyst prepared by the method of the present invention has an obvious bimodal pore structure, large pore volume, large pore diameter and higher macropore ratio of more than 100 nm. It can also be seen from the comparison effect between comparative example 3 and example 1 that, by adopting the method of the present invention, the pore volume and the pore diameter of the obtained carrier are larger, the proportion of macropores is higher, and the addition amount of the pore-enlarging agent can be effectively reduced, which is beneficial to reducing the production cost.
The catalysts of Table 1 were evaluated for activity stability, and the evaluation conditions and results are shown in Table 2 and Table 3, respectively.
TABLE 2 catalyst evaluation conditions
| Properties of crude oil | Middle east residual oil |
| Density (20 ℃ C.)/g-cm -3 | 0.99 |
| (Ni+V)，μg.g -1 | 103 |
| Process conditions | |
| Reaction temperature, deg.C | 380 |
| Partial pressure of hydrogen, MPa | 16 |
| Volumetric space velocity h -1 | 1.0 |
| Hydrogen/oil ratio | 750 |
TABLE 3 catalyst Metal removal Rate (HD (Ni + V))
The results of the evaluation in Table 3 show that the catalyst of the present invention has a higher demetallization activity, a small decrease in activity after a long-term operation, good stability and a high impurity-containing capacity.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. The preparation method of the poor-quality residual oil hydrodemetallization catalyst is characterized by comprising the following steps of: mixing hydrated alumina with a powdery adhesive and an organic pore-enlarging agent, then adding an aqueous solution containing a chemical pore-enlarging agent, ammonia and low carbon alcohol, kneading, molding, drying and roasting, and then loading active metal to obtain a catalyst; the adhesive is synthetic cellulose, the organic pore-enlarging agent is water-soluble organic polymer, and the chemical pore-enlarging agent is boron-containing compound.
2. The method for preparing a poor residue hydrodemetallization catalyst as claimed in claim 1, wherein the water-soluble organic polymer is one or more selected from the group consisting of polyethylene glycol, polyacrylamide, polyvinyl alcohol and crospovidone, and the amount of the added water-soluble organic polymer is 1-6% of the weight of the alumina.
3. The method for preparing a poor quality residual oil hydrodemetallization catalyst according to claim 1, wherein the boron-containing compound is one or more selected from boric acid, metaboric acid, ammonium hydrogen borate, ammonium tetraborate tetrahydrate and ammonium pentaborate tetrahydrate, and the addition amount is 0.3-2% of the weight of alumina calculated by elemental boron.
4. The method for preparing a poor residuum hydrodemetallization catalyst according to claim 1, wherein the amount of ammonia added is 0.05-0.5% by weight of alumina.
5. The method for preparing a poor residuum hydrodemetallization catalyst according to claim 1, wherein the lower alcohol is one or more selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol and glycerol, and the amount of the lower alcohol added is 0.5-5% by weight of the alumina.
6. The method for preparing a poor residue hydrodemetallization catalyst according to claim 1, characterized in that the active metals comprise a first active metal and/or a second active metal, the first active metal is molybdenum and/or tungsten, the second active metal is cobalt and/or nickel, calculated by oxide, the molybdenum and/or tungsten accounts for 2-8% of the total weight of the catalyst, and the cobalt and/or nickel accounts for 0.4-2%.
7. The method for preparing a poor residue hydrodemetallization catalyst according to claim 1, wherein the synthetic cellulose is one or more selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the addition amount is 1-5% by weight of the alumina.
8. The method for preparing a poor residuum hydrodemetallization catalyst according to claim 7, characterized in that the synthetic cellulose has a 2% aqueous viscosity of not less than 50000 mPa-s.
9. The method for preparing a poor residuum hydrodemetallization catalyst according to claim 1, wherein the particle size of the water-soluble organic polymer is 80-400 mesh.
10. The method for preparing a poor residual oil hydrodemetallization catalyst according to claim 1, wherein the forming process is performed by using an oil pressure or hydraulic bar extruder, and the extrusion pressure is 10-30 MPa.
11. The method for preparing a poor residual oil hydrodemetallization catalyst according to claim 1, wherein the roasting temperature is 500-1100 ℃ and the roasting time is 0.5-4 hours.
12. A poor residuum hydrodemetallization catalyst prepared according to the process of any one of claims 1-11.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728335A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of boron-modified alumina carrier |
| CN105983418A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of TiO 2-containing macroporous residual oil hydrodemetallization catalyst |
| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN108786833A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728335A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of boron-modified alumina carrier |
| CN105983418A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of TiO 2-containing macroporous residual oil hydrodemetallization catalyst |
| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN108786833A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst and preparation method thereof |
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