CN111822011B - Carrier and catalyst for hydrodesulfurization and preparation method thereof - Google Patents
Carrier and catalyst for hydrodesulfurization and preparation method thereof Download PDFInfo
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- CN111822011B CN111822011B CN201910308837.5A CN201910308837A CN111822011B CN 111822011 B CN111822011 B CN 111822011B CN 201910308837 A CN201910308837 A CN 201910308837A CN 111822011 B CN111822011 B CN 111822011B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 182
- 239000011148 porous material Substances 0.000 claims abstract description 149
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 14
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 11
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 239000003921 oil Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 VIB group metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/635—0.5-1.0 ml/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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a carrier and a catalyst for hydrodesulfurization and a preparation method thereof. The carrier is an alumina carrier containing an auxiliary agent, and comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels, the auxiliary agent phosphorus and/or boron is distributed in the micron-sized pore channels, and the auxiliary agent titanium is distributed on the surface of the rod-shaped alumina on the outer surface of the carrier. The preparation method of the carrier comprises the following steps: adsorbing a solution containing an auxiliary agent phosphorus and/or boron by using a physical pore-enlarging agent, then kneading and molding the solution and pseudo-boehmite, drying and roasting to obtain a carrier intermediate; immersing the mixture into an ammonium bicarbonate solution, sealing, performing heat treatment, and drying; and spraying a solution containing the auxiliary agent titanium on the outer surface of the impregnated material, drying and roasting to obtain the alumina carrier. The prepared hydrodesulfurization catalyst is suitable for the residual oil hydrodesulfurization treatment process and has the characteristics of good macromolecular diffusion performance, strong metal-containing capacity, high desulfurization capacity and the like.
Description
Technical Field
The invention relates to an alumina carrier, a catalyst and a preparation method thereof, in particular to a catalyst carrier and a catalyst for residual oil hydrodesulfurization and a preparation method thereof.
Background
With the increasing weight and quality of petroleum, petroleum processing is more and more difficult. Heavy oil residues contain a large amount of sulfur, most of which is present in asphaltenes, and are difficult to remove. Hydrodesulfurization as petroleum refining and raw materialThe important technological process in the production of synthetic ammonia is always paid attention by people. However, in recent years, the quality of petroleum is getting heavier and worse, the requirements on the quality of products are stricter, and the requirements on the feeding materials in the subsequent process are more and more strict. In addition, since the 21 st century, people's awareness of environmental protection has been increasing and legislation on environmental protection has become stricter, and NO in exhaust gas discharged from motor vehicles has become more seriousx、SOxAnd the limitation of the aromatic content is more severe. In 2010, a sulfur content of less than 10 μ g/g was required. For the above reasons, hydrodesulfurization techniques for gasoline and diesel are moving toward the processing of high sulfur oils and the production of ultra-low sulfur clean petroleum fuels.
The carrier material used by the existing residual oil hydrodesulfurization catalyst is generally macroporous alumina and modified products thereof. The common preparation method of the macroporous alumina comprises the following steps: physical pore-forming method, high-temperature roasting method and pH value swinging method. The physical pore-forming method has the disadvantages of non-uniform pore channels and easy blockage. US4448896, US4102822 and the like use physical pore-expanding agents such as carbon black, starch and the like to be mixed and kneaded with active alumina or precursors of the alumina to expand the pore diameter of the alumina carrier, and the dosage of the physical pore-expanding agent is more than 10wt% of the alumina.
Because of the limitation of the property of the residual oil hydrodesulfurization catalyst in the prior art, the residual oil hydrodesulfurization catalyst generally only has a desulfurization function and a weak demetallization function, and can only utilize the outer surface of the catalyst to carry out demetallization reaction, and metal precipitates are precipitated in gaps, so that in the residual oil hydrogenation series catalysts, the demetallization agent is required to remove metal to the maximum extent during desulfurization, and the metal content is as low as possible when the residual oil hydrodesulfurization catalyst enters a desulfurizer bed layer, so that the desulfurizer can run for a long period.
CN1107102C discloses a hydrodemetallization and hydrodesulfurization catalyst and a preparation method thereof, wherein a pore-expanding method is adopted by adding carbon black and the acidity of a carrier is adjusted by adding boron. The carrier obtained by the method has a double-peak structure, the first peak is concentrated at about 10nm, the second peak is a pore channel left after the carbon black is burnt out and is concentrated at about 200-500nm, most of the pore channels left by the carbon black are ink bottle openings, the pore channel is not beneficial to the separation of residual oil asphaltene micelles, and the hydrodesulfurization rate is low.
CN1205314C discloses a preparation method of a heavy oil hydrodemetallization and desulfurization catalyst, wherein a carrier is compounded by two kinds of alumina, one of the two kinds of alumina is alumina powder calcined at the high temperature of 1100 ℃, the method can form more pore channels with the diameter of more than 15nm, and the pore channels have penetrability, but are too small for asphaltene micelle, which is not beneficial to residual oil hydrodesulfurization and hydrodemetallization reactions.
The two methods have the defects of small pore channel, difficult metal diffusion and the like, and can not prepare the residual oil hydrotreating catalyst with high desulfurization rate and high metal capacity.
Disclosure of Invention
Aiming at the defects of single function, poor metal capacity and the like of a hydrodesulfurization catalyst in the prior art, the invention provides a carrier and a catalyst for hydrodesulfurization and a preparation method thereof. The hydrodesulfurization catalyst prepared by the carrier has the characteristics of good macromolecular diffusion performance, strong metal capacity, high desulfurization capacity and the like. The hydrodesulfurization catalyst is particularly suitable for residual oil hydrodesulfurization treatment process.
The hydrodesulfurization catalyst carrier is an auxiliary agent-containing alumina carrier, the auxiliary agent-containing alumina carrier comprises main alumina and rod-shaped alumina, the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and the micron-sized pore channels with the pore diameter D of 3-7 mu m, the auxiliary agent is phosphorus and/or boron and titanium, the auxiliary agent phosphorus and/or boron is distributed in the micron-sized pore channels, the auxiliary agent titanium is distributed on the rod-shaped alumina surface on the outer surface of the carrier, the rod-shaped alumina has the length of 1-9 mu m and the diameter of 80-260 nm.
The micron-sized pore canal in the invention refers to a micron-sized pore canal with the pore diameter D of 3-7 μm.
The auxiliary agent phosphorus and/or boron is distributed in the micron-sized pore channels, and means that the auxiliary agent phosphorus and/or boron is mainly distributed on the surfaces of the micron-sized pore channels (including rod-shaped alumina distributed in the micron-sized pore channels).
The auxiliary agent is phosphorus and/or boron and titanium, and the weight content of the auxiliary agent phosphorus and/or boron in the carrier is 0.5-2.0% and the weight content of the auxiliary agent titanium in the carrier is 0.2-0.5% in terms of oxide.
In the carrier, the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore canal. The rod-shaped alumina distributed on the outer surface of the main alumina and in the micron-sized pore channels accounts for more than 95 percent of the total weight of all the rod-shaped alumina, and preferably more than 97 percent.
In the carrier, the length of the rod-shaped alumina in the micron-sized pore channels is mainly 0.3D-0.9D (which is 0.3-0.9 time of the diameter of the micron-sized pore channels), namely the length of more than 85 percent of the rod-shaped alumina in the micropores is 0.3D-0.9D; the length of the rod-shaped alumina on the outer surface is mainly 3-8 μm, that is, the length of more than 85% of the rod-shaped alumina on the outer surface is 3-8 μm.
Wherein, in the micron-scale pore channels of the main alumina, the rod-shaped alumina is distributed in a disordered and mutually staggered state.
Wherein at least one end of at least part of the rod-shaped alumina is attached to the micron-sized pore channel wall of the main body, and preferably at least one end of at least part of the rod-shaped alumina is bonded to the micron-sized pore channel wall and is integrated with the main body alumina. Further preferably, at least one end of the rod-shaped alumina in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel, and is integrated with the main alumina.
Wherein the rod-like aluminas are distributed on the outer surface of the main alumina in a disordered and staggered state.
Wherein one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina, and preferably, one end of at least part of the rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina. Further preferably, one end of the rod-shaped alumina on the outer surface of the main body alumina is bonded to the outer surface of the main body alumina, and the other end thereof is protruded outward to be integrated with the main body.
In the carrier, the coverage rate of the rod-shaped alumina in the micron-sized pore channels of the main alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the inner surface of the micron-sized pore channels of the main alumina, which is occupied by the rod-shaped alumina, in the inner surface of the micron-sized pore channels of the main alumina. The coverage rate of the rod-shaped alumina on the outer surface of the main body alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the outer surface of the main body alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main body alumina.
The carrier of the invention has the following properties: the specific surface area is 190-280m2(iv)/g, pore volume of 0.8-1.6mL/g, crush strength of 10-20N/mm.
In the carrier of the invention, the pores formed by the rod-shaped alumina in a disordered mutual staggering manner are concentrated between 100-600 nm.
The pore distribution of the carrier of the invention is as follows: the pore volume of the pores with the pore diameter of less than 10nm is less than 10 percent of the total pore volume, the pore volume of the pores with the pore diameter of 10-30nm is 45-70 percent of the total pore volume, the pore volume of the pores with the pore diameter of 100-600nm is 10-20 percent of the total pore volume, and the pore volume of the pores with the pore diameter of more than 1000nm is less than 5 percent.
The second aspect of the present invention provides a method for preparing a hydrodesulfurization catalyst support, comprising:
(1) adsorbing a solution containing an auxiliary agent phosphorus and/or boron by using a physical pore-enlarging agent, kneading and molding pseudo-boehmite and the physical pore-enlarging agent adsorbing the auxiliary agent, and drying and roasting a molded product to obtain a carrier intermediate;
(2) immersing the carrier intermediate into an ammonium bicarbonate solution, then carrying out sealing heat treatment, and drying the materials after the heat treatment;
(3) and (3) spraying and dipping the outer surface of the material in the step (2) by using a solution containing an auxiliary agent titanium, and drying and roasting the dipped material to obtain the alumina carrier.
In the preparation method of the carrier, the properties of the carrier intermediate in the step (1) are as follows: the specific surface area is 150-240m2The pore volume is 0.7-1.4mL/g, and the pore distribution is as follows: pore diameter of 10-30nmThe occupied pore volume is 40-60% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-600nm is 5-10% of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 3 mu m (preferably the pores with the pore diameter of 3-7 mu m) is 5-15% of the total pore volume.
In the preparation method of the carrier, in the step (1), the physical pore-enlarging agent can be one or more of activated carbon, charcoal and wood dust, the particle size of the added physical pore-enlarging agent is selected according to micron-sized pore canals of the alumina carrier intermediate, wherein the particle size of the physical pore-enlarging agent is preferably about 3-7 mu m, and the addition amount of the physical pore-enlarging agent is 10-20 wt% of the weight of the alumina carrier intermediate. The kneading molding can be carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like can be added according to needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the extrusion assistant agent is a substance which is beneficial to extrusion forming, such as sesbania powder and the like. The drying and roasting conditions of the formed product are as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
In the preparation method of the carrier, in the step (1), the physical pore-expanding agent adsorbs the solution containing the auxiliary agent phosphorus and/or boron, and the using amount of the solution containing the auxiliary agent phosphorus and/or boron is 30-50% of the saturated water absorption amount of the physical pore-expanding agent. When the solution containing the auxiliary agent is prepared, the adopted phosphorus source can be phosphoric acid or phosphate, and the phosphate can be one or more of ammonium hydrogen phosphate and diammonium hydrogen phosphate; the boron source used may be boric acid or a borate salt, which may be ammonium borate. The mass percentage of the auxiliary agent in the solution is 1-6 percent calculated by oxide.
In the preparation method of the carrier, the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the carrier intermediate in the step (1) is 3:1-6:1, and the mass concentration of the ammonium bicarbonate solution is 10% -20%.
In the preparation method of the carrier, the sealing heat treatment temperature in the step (2) is 110-.
In the preparation method of the carrier, the step (2) is preferably carried out before sealing heat treatment, the sealing pretreatment is carried out at the pretreatment temperature of 60-100 ℃ for 2-4 hours at constant temperature, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is lower than that before the pretreatment by at least 3 ℃/min, preferably at least 5 ℃/min.
In the preparation method of the carrier, the drying temperature in the step (2) is 100-160 ℃, and the drying time is 6-10 hours.
In the preparation method of the carrier, the solution containing the auxiliary agent titanium in the step (3) is an ethanol solution containing titanate, the titanate is selected from one or a mixture of more of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, n-butyl titanate and tetraisobutyl titanate, the solution dosage is 10-20% of the saturated water absorption of the material in the step (2), and the mass percentage content of the auxiliary agent titanium in the solution is 1-5% by weight of oxide.
In the preparation method of the carrier, the drying temperature in the step (3) is 160 ℃ and the drying time is 6-10 hours, the roasting temperature is 600 ℃ and 750 ℃ and the roasting time is 4-6 hours.
In the method of the invention, the carrier prepared in the step (3) and the carrier intermediate in the step (1) have the pore diameter of 10-30nm and the pores with the diameter of 100-600nm, and the former is more concentrated than the latter.
The third aspect of the invention provides a hydrodesulfurization catalyst, which comprises a carrier and an active metal component, wherein the carrier adopts the carrier.
In the hydrodesulfurization catalyst, the active metal components are VIB group metals and VIII group metals. The VIB group metal is selected from one or more of W, Mo, and the VIII group metal is selected from one or more of Co and Ni. Based on the weight of the catalyst, the content of the active metal oxide is 10 to 25 percent, preferably the content of the VIB group metal oxide is 6.5 to 18.0 percent, and the content of the VIII group metal oxide is 1.5 to 7.0 percent
The hydrodesulfurization catalyst of the present invention can be prepared by a conventional method such as impregnation, kneading, etc., and preferably by impregnation. The impregnation process is as follows: the carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. After the active metal components are impregnated, the hydrodesulfurization catalyst is obtained after drying and roasting. The drying condition is that the drying is carried out for 1 to 5 hours at the temperature of 100-130 ℃; the roasting condition is roasting at 400-550 ℃ for 2-10 hours.
The hydrodesulfurization catalyst is suitable for a residual oil hydrodesulfurization treatment process, and has high sulfur removal rate and high metal and nitrogen removal rate.
Compared with the prior art, the invention has the following advantages:
1. the carrier of the invention makes full use of the micron-scale pore channels of the alumina intermediate, and the rod-shaped alumina is distributed in the micron-scale pore channels in a staggered way in a disordered way, so that on one hand, the penetrability of the micron-scale pore channels is maintained, the specific surface area of the carrier is improved, the mechanical strength is enhanced, on the other hand, a certain hole expanding effect is performed on the nano-scale pore channels of the carrier intermediate, and the penetrability and the uniformity of the nano-scale pore channels are further promoted. Therefore, the alumina carrier of the invention overcomes the problem that the large aperture, the specific surface area and the mechanical strength are not compatible caused by adopting a physical pore-expanding agent.
2. In the process of preparing the carrier, the physical pore-enlarging agent adsorbs the solution containing the auxiliary agent, and then the solution is kneaded with the pseudo-boehmite, so that the auxiliary agent components are mainly distributed on the surfaces of micron-sized pore channels, and the auxiliary agent is the existence of phosphorus and/or boron and the special distribution state of the phosphorus and/or boron, which is more favorable for the hydrodesulfurization of the catalyst and has better activity.
3. In the process of preparing the carrier, the titanium-containing solution is used for unsaturated spraying and dipping the alumina carrier, and the rodlike alumina on the surface of the carrier is subjected to titanium modification, so that the rodlike alumina on the surface of the carrier forms a titanium-aluminum composite oxide, the properties of the rodlike alumina on the surface are modulated and are matched with each other, and the hydrodesulfurization activity of the catalyst is improved.
4. In the process of preparing the carrier, the carrier is pretreated at a certain temperature before sealing heat treatment, the pretreatment condition is relatively mild, and NH is slowly formed on the outer surface of the alumina carrier in a sealed and hydrothermal mixed atmosphere of carbon dioxide and ammonia gas4Al(OH)2CO3Crystal nuclei, raising the reaction temperature NH during the post-heat treatment4Al(OH)2CO3The crystal nucleus continues to grow evenly to make rod-shaped NH4Al(OH)2CO3Having uniform diameter and length while increasing rod-like NH4Al(OH)2CO3Coverage on the outer surface of the alumina intermediate and the inner surface of the micron-sized pore channel.
5. The alumina carrier is particularly suitable for preparing a hydrodesulfurization catalyst, has higher hydrodesulfurization activity and hydrodenitrogenation and demetalization activities when being used for residual oil hydrodesulfurization reaction, has good stability, and can prolong the running period of a device.
Drawings
FIG. 1 is an SEM photograph of a cut surface of a support obtained in example 3;
wherein the reference numbers are as follows: 1-main alumina, 2-rod-shaped alumina and 3-micron pore canal.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction.
Application N2Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 40nm is obtained according to a BJH model.
Mercury pressing method: use of mercury intrusion instrument to characterize the pores of the carriers of the examples and comparative examplesThe diameter distribution is specifically operated as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution ratio of pore diameter of 100nm or more is measured by mercury intrusion method.
A scanning electron microscope is used for representing the microstructure of the alumina carrier, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.
Example 1
Weighing 25 g of activated carbon with the particle size of 6 microns, spraying and soaking the activated carbon by using 7.5mL of ammonium hydrogen phosphate solution with the mass concentration of 28%, uniformly mixing the sprayed and soaked activated carbon with 260 g of pseudo-boehmite dry glue powder (produced by Wenzhou Jingjing alumina Co., Ltd.) and 8 g of sesbania powder, adding a proper amount of acetic acid aqueous solution with the mass concentration of 1.5%, kneading, extruding into strips, drying the formed product at 110 ℃ for 6 hours, and roasting the dried product at 700 ℃ for 5 hours in an air atmosphere to obtain an alumina carrier intermediate ZA 1.
Weighing 1100 g of the alumina carrier intermediate ZA, placing the alumina carrier intermediate ZA into 500 g of ammonium bicarbonate solution, sealing the mixed material in a high-pressure kettle, heating to 100 ℃ at a speed of 15 ℃/min, keeping the temperature for 3 hours, heating to 140 ℃ at a speed of 10 ℃/min, keeping the temperature for 6 hours, and drying the carrier at 100 ℃ for 6 hours.
Placing the materials in a spray-dipping roller, using 15mL ethanol solution of tetraethyl titanate with the mass concentration of 3% of titanium dioxide to carry out unsaturated spray-dipping on the materials, drying the spray-dipped materials for 6 hours at 120 ℃, and roasting the dried materials for 6 hours at 700 ℃ to obtain the alumina carrier A1, wherein the properties of the carrier are shown in Table 1. P in the alumina carrier A12O51wt% of titanium dioxide, 0.4wt% of titanium dioxide, and the length of rod-like alumina in micron-sized pore channel is 1.8-5.5 μm as main bodyThe length of the rod-shaped alumina on the outer surface of the alumina is 3.5-8.0 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 86%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 83%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 100-400 nm.
Example 2
In the same manner as in example 1 except that the activated carbon was changed to charcoal having a particle size of 4 μm, the amount of charcoal added was 29 g, the ammonium hydrogenphosphate solution was changed to a phosphoric acid solution in an amount of 8.5mL, and the mass concentration of the solution was 30%, to obtain an alumina support intermediate ZA 2. The mass of the ammonium bicarbonate solution is 600 grams, and the mass concentration of the ammonium bicarbonate solution is 17.5 percent. The sealing pretreatment temperature is 90 ℃, the treatment time is 2 hours, the heat treatment temperature is 110 ℃, the treatment time is 8 hours, the tetraethyl titanate is changed into the tetramethyltitanate, the solution dosage is 20ml, the mass concentration of the titanium dioxide in the solution is 1%, and the prepared alumina carrier A2 has the properties shown in Table 1. P in the alumina carrier A22O5The content is 1.5wt%, the content of titanium dioxide is 0.2wt%, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 1-3.5 mu m, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3.5-8 mu m, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 80%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 78%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 100-400 nm.
Example 3
In the same manner as in example 1 except that the activated carbon was changed to wood chips having a particle size of 7 μm, the amount of the wood chips added was 21 g, the amount of the ammonium hydrogen phosphate solution was 7mL, and the mass concentration of the solution was 25%, thereby obtaining an alumina carrier intermediate ZA 3. The mass of the ammonium bicarbonate solution is 300 g, and the mass concentration of the ammonium bicarbonate solution is 20%. The heating rate before the sealing pretreatment is 11 ℃/min, the heating rate after the sealing pretreatment is 5 ℃/min, the heat treatment temperature is 150 ℃, the treatment time is 4 hours, the dosage of the tetraethyl titanate solution is 10ml, the mass concentration of the titanium dioxide in the solution is 5%, and the prepared alumina carrier A3 has the properties shown in Table 1. P in the alumina carrier A32O5The content of the alumina is 0.8wt%, the content of the titanium dioxide is 0.5wt%, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 2.0-6.0 mu m, the length of the rod-shaped alumina on the outer surface of the main body alumina is mainly 3-8 mu m, the coverage rate of the rod-shaped alumina on the outer surface of the main body alumina is about 81%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel is about 84%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 200-500 nm.
Example 4
As in example 1, the temperature was raised to 140 ℃ at a rate of 15 ℃/min and the heat treatment was carried out without any pretreatment before the heat treatment. The alumina carrier A4 of the present invention was prepared, and the properties of the carrier are shown in Table 1. P in the alumina carrier A42O5The content is 1wt%, the content of titanium dioxide is 0.4wt%, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 1.8-5.5 mu m, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3.5-8.0 mu m, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 75%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 79%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 100-400 nm.
Comparative example 1
Similar to example 1, except that the ammonium bicarbonate solution was changed to ammonium carbonate solution during the preparation of the alumina-based support, alumina support A5 was obtained, and the properties of alumina support A5 are shown in Table 1.
Comparative example 2
Similar to example 1, except that the ammonium bicarbonate solution was changed to sodium bicarbonate solution during the preparation of the alumina-based support, alumina support A6 was obtained, and the properties of alumina support A6 are shown in Table 1.
TABLE 1 Properties of the alumina support intermediate and the alumina support
| Example 1 | Example 1 | Example 2 | Example 2 | Example 3 | Example 3 | |
| Numbering | ZA1 | A1 | ZA2 | A2 | ZA3 | A3 |
| Specific surface area, m2/g | 189 | 198 | 193 | 201 | 186 | 223 |
| Pore volume, mL/g | 0.92 | 1.07 | 0.91 | 1.03 | 0.95 | 1.01 |
| Pore distribution:, v% | ||||||
| Less than 10nm | - | 9 | - | 7 | - | 8 |
| 10-30nm | 45 | 52 | 43 | 54 | 43 | 53 |
| 100-600nm | 9 | 20 | 10 | 21 | 7 | 19 |
| Greater than 1000nm | - | 3 | - | 4 | - | 3 |
| Over 5 mu m | 10 | Is free of | 9 | Is free of | 8 | Is free of |
| Crush strength, N/mm | 10.7 | 13.4 | 10.7 | 12.9 | 11.2 | 12.6 |
Table 1 shows the properties of the alumina carrier intermediate and the alumina carrier
| Example 4 | Comparative example 1 | Comparative example 2 | |
| Numbering | A4 | A5 | A6 |
| Specific surface area, m2/g | 201 | 174 | 181 |
| Pore volume, mL/g | 1.02 | 0.77 | 0.75 |
| Pore distribution:, v% | |||
| Less than 10nm | 8 | 28 | 27 |
| 10-30nm | 48 | 30 | 35 |
| 100-600nm | 17 | 16 | 16 |
| Greater than 1000nm | 3 | - | - |
| Over 3 mu m | Is free of | 8 | 7 |
| Crush strength, N/mm | 12.8 | 9.7 | 9.9 |
Example 5
This example uses the aluminas obtained in the above examples and comparative examples as supports to prepare hydrodesulfurization catalysts.
Weighing the alumina carrier intermediate ZA 1100 g of example 1, adding 150mL of Mo-Ni-NH3Solution (according to MoO content in the final catalyst)312.5wt% and NiO 4.0 wt%) for 2 hours, filtering off the excess solution, drying at 120 ℃ for 4 hours, and calcining at 550 ℃ for 5 hours to obtain the hydrodesulfurization catalyst C0.
Catalysts C1-C6 were prepared in the same manner as catalyst C0 except that the intermediate ZA1 on the alumina support was replaced with the alumina supports A1-A6 prepared in examples 1-4 and comparative examples 1-2, respectively, to obtain hydrodesulfurization catalysts C1-C6.
Example 6
The following examples illustrate the catalytic performance of hydrodesulfurization catalysts C0-C6.
Raw oil listed in Table 2 is used as a raw material, the catalytic performance of C0-C6 is evaluated on a fixed bed residual oil hydrogenation reaction device, the catalyst is a strip with the length of 2-3 mm, the reaction temperature is 380 ℃, the volume ratio of hydrogen to oil is 1000, and the liquid hourly volume space velocity is 0.49h-1The hydrogen partial pressure was 14 MPa. The catalyst was run for 2500 hours and the impurity removal properties are shown in Table 3.
TABLE 2 Properties of the feed oils
| Item | |
| Density (20 ℃ C.), g/cm3 | 0.97 |
| S，wt% | 3.4 |
| N，wt% | 0.36 |
| Ni，µg/g | 21.5 |
| V，µg/g | 62.4 |
| CCR，wt% | 11.5 |
TABLE 3 evaluation results of catalysts obtained in inventive examples and comparative examples
| Hydrodesulfurization catalyst | C0 | C1 | C2 | C3 | C4 | C5 | C6 |
| Desulfurization degree, wt% | 64.1 | 95.1 | 94.7 | 94.6 | 91.2 | 71.5 | 73.8 |
| Denitrification rate, wt% | 52.3 | 75.1 | 74.4 | 76.0 | 72.9 | 63.7 | 65.3 |
| Removing Ni + V, wt% | 51.4 | 73.1 | 73.7 | 73.1 | 69.7 | 54.6 | 52.0 |
It can be seen from the results in table 3 that the hydrodesulfurization catalyst of the present invention has a high sulfur removal rate and at the same time has a high metal and nitrogen removal rate. The desulfurization and denitrification rates of the catalysts prepared in comparative examples 1 and 2 were significantly lower than the removal rate of the catalyst of the present invention.
Claims (28)
1. A hydrodesulfurization catalyst carrier is an auxiliary agent-containing alumina carrier, and the auxiliary agent-containing alumina carrier comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and the micron-sized pore channels with the pore diameter D of 3-7 mu m, the auxiliary agent is phosphorus and/or boron and titanium, the auxiliary agent phosphorus and/or boron is distributed in the micron-sized pore channels, the auxiliary agent titanium is distributed on the surface of the rod-shaped alumina on the outer surface of the carrier, the rod-shaped alumina is 1-9 mu m in length and 80-260 nm in diameter; the pore distribution of the carrier is as follows: the pore volume occupied by the pores with the pore diameter of less than 10nm is less than 10 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 10-30nm is 45-70 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-600nm is 10-20 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 1000nm is less than 5 percent of the total pore volume.
2. The carrier of claim 1, wherein: the auxiliary agent is phosphorus and/or boron and titanium, and the weight content of the auxiliary agent phosphorus and/or boron in the carrier is 0.5-2.0% and the weight content of the auxiliary agent titanium in the carrier is 0.2-0.5% in terms of oxide.
3. The carrier of claim 1, wherein: the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore channels.
4. The carrier of claim 1, wherein: in the carrier, more than 85 percent of the rod-shaped alumina in the micron-sized pore channels by weight has the length of 0.3D-0.9D; the rod-shaped alumina on the outer surface has a length of 3 to 8 μm of 85% by weight or more.
5. The carrier of claim 1, wherein: in the micron-sized pore channels of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; at least one end of at least part of the rod-shaped alumina is attached to the micron-sized pore channel wall of the main body.
6. The vector of claim 5, wherein: in the micron-sized pore channels of the main alumina, at least one end of at least part of rod-shaped alumina is combined on the wall of the micron-sized pore channel and is integrated with the main alumina.
7. The vector of claim 5, wherein: at least one end of the rod-shaped alumina in the micron-sized pore channel is combined on the wall of the micron-sized pore channel and is integrated with the main alumina.
8. The vector according to claim 1 or 5, wherein: on the outer surface of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; at least one end of the rod-shaped alumina is attached to the outer surface of the main alumina.
9. The carrier of claim 6, wherein: on the outer surface of the main alumina, one end of at least partial rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina.
10. The carrier of claim 6, wherein: one end of the rod-shaped alumina on the outer surface of the main alumina is bonded on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main body.
11. The carrier of claim 1, wherein: in the carrier, the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina accounts for 70-95 percent; the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is 70-95%.
12. The carrier of claim 1, wherein: in the carrier, pores formed by the rod-shaped alumina in a disordered staggered manner are concentrated between 100-600 nm.
13. The carrier of claim 1, wherein: the properties of the vector are as follows: the specific surface area is 190-2(iv)/g, pore volume of 0.8-1.6mL/g, crush strength of 10-20N/mm.
14. A method of making a hydrodesulfurization catalyst support as defined in any one of claims 1 to 13 comprising:
(1) adsorbing a solution containing an auxiliary agent phosphorus and/or boron by using a physical pore-enlarging agent, kneading and molding pseudo-boehmite and the physical pore-enlarging agent adsorbing the auxiliary agent, and drying and roasting a molded product to obtain a carrier intermediate;
(2) immersing the carrier intermediate into an ammonium bicarbonate solution, then carrying out sealing heat treatment, and drying the materials after the heat treatment;
(3) spraying and dipping the outer surface of the material in the step (2) by using a solution containing an auxiliary agent titanium, and drying and roasting the dipped material to obtain an alumina carrier;
the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the carrier intermediate in the step (1) is 3:1-6:1, and the mass concentration of the ammonium bicarbonate solution is 10% -20%; the sealing heat treatment temperature is 110-160 ℃, and the constant temperature treatment time is 4-8 hours; before the sealing heat treatment, sealing pretreatment is carried out, the pretreatment temperature is 60-100 ℃, and the constant temperature treatment time is 2-4 hours.
15. The method of claim 14, wherein: the carrier intermediate in the step (1) has the following properties: ratio ofSurface area of 150-240m2The pore volume is 0.7-1.4mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameters of 10-30nm is 40% -60% of the total pore volume, the pore volume occupied by the pores with the pore diameters of 100-600nm is 5% -10% of the total pore volume, and the pore volume occupied by the pores with the pore diameters of more than 3 mu m is 5% -15% of the total pore volume.
16. The method of claim 15, wherein: and (2) the pore volume occupied by the pores with the pore diameter of 3-7 mu m of the carrier intermediate in the step (1) is 5% -15% of the total pore volume.
17. A method according to claim 14 or 15, characterized by: the physical pore-expanding agent is one or more of activated carbon, charcoal and wood chips, and the addition amount of the physical pore-expanding agent is 10-20 wt% of the weight of the alumina carrier intermediate; the drying and baking conditions of the molded product were as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours.
18. A method according to claim 14 or 15, characterized by: in the step (1), the physical pore-expanding agent is adsorbed with a solution containing the auxiliary agent phosphorus and/or boron, and the dosage of the solution containing the auxiliary agent phosphorus and/or boron is 30-50% of the saturated water absorption capacity of the physical pore-expanding agent.
19. A method according to claim 14 or 15, characterized by: the heating rate of the sealing heat in the step (2) is 5-20 ℃/min.
20. A method according to claim 14 or 15, characterized by: in the step (2), the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min lower than that before the pretreatment.
21. The method of claim 20, wherein: the temperature rise rate after the pretreatment is lower than that before the pretreatment by at least 5 ℃/min.
22. A method according to claim 14 or 15, characterized by: the drying temperature in the step (2) is 100-160 ℃, and the drying time is 6-10 hours.
23. A method according to claim 14 or 15, characterized by: the solution containing the auxiliary agent titanium in the step (3) is an ethanol solution containing titanate, the titanate is one or a mixture of more of tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, n-butyl titanate and tetraisobutyl titanate, the dosage of the solution is 10-20% of the saturated water absorption of the material in the step (2), and the mass percentage of the auxiliary agent titanium in the solution is 1-5% by weight of oxide.
24. A method according to claim 14 or 15, characterized by: the drying temperature in the step (3) is 160 ℃ and the drying time is 6-10 hours, the roasting temperature is 600 ℃ and 750 ℃ and the roasting time is 4-6 hours.
25. A hydrodesulphurisation catalyst comprising an active metal component and a support according to any of claims 1 to 13.
26. The catalyst as set forth in claim 25, wherein: the active metal component is VIB group metal and VIII group metal, the VIB group metal is selected from one or two of Mo and W, and the VIII group metal is selected from one or two of Co and Ni; the content of active metal is 10.0-25.0% calculated by metal oxide based on the weight of the catalyst.
27. The catalyst of claim 26, wherein: based on the weight of the catalyst, the content of VIB group metal is 6.5-18.0 percent calculated by metal oxide, and the content of VIII group metal is 1.5-7.0 percent calculated by metal oxide.
28. A process for the hydrotreatment of a residual oil, characterized in that a hydrodesulphurization catalyst as claimed in any of claims 25 to 27 is used.
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