CN110935467B - Preparation method of hydrotreating catalyst - Google Patents
Preparation method of hydrotreating catalyst Download PDFInfo
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- CN110935467B CN110935467B CN201811114187.2A CN201811114187A CN110935467B CN 110935467 B CN110935467 B CN 110935467B CN 201811114187 A CN201811114187 A CN 201811114187A CN 110935467 B CN110935467 B CN 110935467B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 128
- 239000011148 porous material Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 20
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- -1 VIB group metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 9
- 229910000480 nickel oxide Inorganic materials 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 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
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical group O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a hydrotreating catalyst, which comprises the following steps: (1) mixing a macroporous alumina carrier, ammonium bicarbonate and water, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain a carrier I, wherein the carrier I is an alumina carrier with a surface growing rod-shaped structure; (2) supersaturating a hydrogenation active component impregnation solution I to impregnate a carrier I, and then drying and roasting to obtain a carrier II; (3) and (3) unsaturated spraying the hydrogenation active component impregnation liquid II to impregnate the carrier II, and then drying and roasting to prepare the hydrogenation catalyst. The catalyst prepared by the method has the advantages that the active metal content of the surface rod-shaped structure is high, the activity is high, meanwhile, an open pore channel is formed in the surface rod-shaped structure, the metal deposition resistance and the carbon deposition resistance of the catalyst are improved, and the method is suitable for the hydrotreating process of heavy oil.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a method for hydrotreating a catalyst, which is particularly suitable for the field of residue hydrogenation.
Background
With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. The hydrodemetallization catalyst mainly removes metal impurities including nickel and vanadium in raw oil, so as to protect downstream catalysts from losing activity due to deposition of a large amount of metals. Hydrodemetallization catalysts generally consist of an alumina support carrying an active metal component. The carrier is used as a framework of the catalyst, reaction channels and surfaces are provided, and meanwhile, the active metal can be highly dispersed, so that the channel structure of the carrier has an important influence on the reaction performance of the catalyst.
CN101890372A discloses an alumina carrier and a preparation method thereof. The alumina carrier is aluminum hydroxide gel prepared by a fused salt super-solubilization micelle method as a raw material, and the gel contains a surfactant and hydrocarbon components, so that after molding and roasting, nano alumina particles formed by dehydrating polymerized aluminum hydroxide still have a rod-like basic structure and are randomly stacked into a frame structure. The process of preparing the macroporous alumina carrier by the technology is complex, in addition, the alumina with the rod-like structure prepared by the technology is in disordered accumulation, the formed pore channel is large, and although the diffusion of macromolecules such as colloid, asphaltene and the like is facilitated, the time for reaction molecules to stay in the pore channel of the catalyst is short, so that the activity of the catalyst is low.
CN106268969A discloses a catalyst carrier, a preparation method thereof and a demetallization catalyst thereof. The catalyst carrier is formed by stacking a plurality of nano rod-shaped alumina monomers, the catalyst carrier is provided with open pore channels, the length of each nano rod-shaped alumina monomer is 100-500nm, and the diameter of each nano rod-shaped alumina monomer is 10-50 nm. The catalyst carrier is formed by stacking a plurality of nano-rod-shaped alumina monomers, the formed pore channel is large, the diffusion of macromolecules such as colloid, asphaltene and the like is facilitated, and the defect that the activity of the catalyst is low due to the fact that reaction molecules stay in the pore channel of the catalyst for a short time is also existed.
CN102861617A discloses a preparation method of an alumina carrier with a double-pore structure. Weighing a certain amount of pseudo-boehmite dry glue powder, uniformly mixing the pseudo-boehmite dry glue powder with a proper amount of peptizer and extrusion aid, then adding a proper amount of ammonium bicarbonate aqueous solution into the materials, kneading the obtained materials into a plastic body, extruding the plastic body into strips, and placing the formed materials into a sealed container to be subjected to hydrothermal treatment and then roasting to obtain the alumina carrier. The pore channels of the alumina carrier prepared by the technology are uniformly distributed in the radial direction of the catalyst, and in the process of the hydrogenation demetallization reaction, metal impurities such as nickel, vanadium and the like in a metal compound are deposited on the surface layer and the near surface layer of the catalyst, so that the pore channels of the catalyst are blocked, and the catalyst is inactivated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst, the catalyst prepared by the method has high active metal content and high activity in a surface rod-shaped structure, and meanwhile, the surface rod-shaped structure forms an open pore channel, so that the metal deposition resistance and carbon deposition resistance of the catalyst are improved, and the method is suitable for the hydrotreating process of heavy oil.
The preparation method of the hydrotreating catalyst comprises the following steps:
(1) mixing a macroporous alumina carrier, ammonium bicarbonate and water, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain a carrier I, wherein the carrier I is an alumina carrier with a surface growing rod-shaped structure;
(2) supersaturating a hydrogenation active component impregnation solution I to impregnate a carrier I, and then drying and roasting to obtain a carrier II;
(3) and (3) unsaturated spraying the hydrogenation active component impregnation liquid II to impregnate the carrier II, and then drying and roasting to prepare the hydrogenation catalyst.
In the method, the properties of the macroporous alumina carrier in the step (1) are as follows: the specific surface area is 150-230m2The pore volume is 0.7-0.9mL/g, and the average pore diameter is 10-30 nm; the preferred pore size distribution is as follows: the pore volume of pores with the diameter of less than 8nm accounts for less than 50 percent of the total pore volume, the pore volume of pores with the diameter of 8-20nm accounts for 30-50 percent of the total pore volume, the pore volume of pores with the diameter of more than 100nm accounts for less than 15 percent of the total pore volume, the pore volume of pores with the diameter of more than 1000nm accounts for less than 2 percent of the total pore volume, and further the pore volume of pores with the diameter of more than 1000nm accounts for less than 1 percent of the total pore volume; the macroporous alumina carrier can be prepared by a commercial product or a conventional method, and the pore-expanding method can be a conventional method, such as adding a pore-expanding agent. In the preparation method, the pore-expanding agent in the step (1) is one or a mixture of carbon black powder, wood chips, polyvinyl alcohol and water-soluble starch. The particle size of the physical pore-enlarging agent is less than 1 mu m, preferably less than 800 nm. The addition amount of the pore-expanding agent is 1 to 3 weight percent of the weight of the alumina.
In the method of the present invention, the preparation method of the macroporous alumina carrier in step (1) may adopt the following method: kneading the pseudo-boehmite and the pore-expanding agent for molding, drying and roasting the molded product to obtain the alumina carrier. The kneading molding is 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 the needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the addition amount of the peptizing agent is 0.5-3 wt% of the weight of the alumina carrier. The extrusion aid is sesbania powder; the addition amount of the extrusion aid is 0.1-0.5 wt% of the weight of the alumina carrier. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere. The shape of the macroporous alumina carrier can be the shape of a conventional alumina carrier, such as a sphere, the particle diameter of the macroporous alumina carrier is generally 0.5-8.0mm, such as a strip shape, a clover shape and the like, the diameter of the macroporous alumina carrier is about 0.2-3.0mm, and the length of the macroporous alumina carrier is about 0.5-8.0 mm.
In the method of the invention, the ammonium bicarbonate and the macroporous alumina carrier in the step (1) are Al2O3The mass ratio of the ammonium bicarbonate solution to the water is 2.5:1:5-5.0:1:20, and the ammonium bicarbonate can be added independently or mixed with the water firstly and added in the form of an ammonium bicarbonate solution.
In the method of the present invention, the sealing heat treatment conditions in step (1) are as follows: the temperature is 120-160 ℃, the constant temperature treatment time is 4-8 hours, and the heating rate is 5-20 ℃/min.
In the method, step (1) is preferably carried out before sealing heat treatment, sealing pretreatment is carried out, the pretreatment temperature is 60-100 ℃, the constant-temperature treatment time is 2-4 hours, the temperature rise rate before pretreatment is 10-20 ℃/min, the temperature rise rate after pretreatment is 5-10 ℃/min, and the temperature rise rate after pretreatment is at least 3 ℃/min, preferably at least 5 ℃/min lower than that before pretreatment.
In the method of the invention, the drying temperature in the step (1) is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-750 ℃, and the roasting time is 4-6 hours.
In the method, the carrier I is an alumina carrier with a surface growing rod-shaped structure, and comprises main alumina and rod-shaped alumina, wherein at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina carrier, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm.
In the method of the invention, in the carrier I, the alumina with a rod-shaped structure is basically distributed on the outer surface of the main alumina. Wherein the length of the rod-shaped alumina distributed on the outer surface of the main alumina is 3-8 μm, namely, the length of more than 85% of the rod-shaped alumina on the outer surface of the main alumina is 3-8 μm. Wherein, the alumina with a rod-shaped structure on the outer surface of the main alumina carrier is randomly and mutually crossly distributed. 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 alumina having a rod-like structure on the outer surface of the main alumina is bonded to the outer surface of the main alumina, and the other end thereof is protruded outward to be integrated with the main alumina.
In the method of the invention, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina of the carrier I is 70-95%, wherein the coverage rate refers to the percentage of the surface of the main alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main alumina.
In the method of the present invention, the properties of the vector I are as follows: the specific surface area is 140-250m2The pore volume is 0.8-1.0mL/g, the diameters of several pores are 10-50nm, 100-500nm and 500-1000nm, and the crushing strength is 110-140N/cm.
In the method, the hydrogenation active component impregnation liquid is a solution containing VIB and/or VIII group metals, wherein the VIB group metals are molybdenum and/or tungsten, and the VIII group metals are cobalt and/or nickel; the hydrogenation active component impregnation liquid can be one of an acid solution, an aqueous solution or an ammonia solution containing the hydrogenation active component.
In the method, the content of the VIB group metal in the hydrogenation active component impregnating solution I in the step (2) is 6.5-15.0g/100ml calculated by metal oxides, and the content of the VIII group metal is 1.5-3.5g/100ml calculated by metal oxides. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
In the method, the content of the VIB group metal in the hydrogenation active component impregnating solution II in the step (3) is 0.8-1.5g/100ml calculated by metal oxide, and the content of the VIII group metal is 0.3-0.6g/100ml calculated by metal oxide. The dosage of the active component impregnation liquid II is 8-15% of the saturated water absorption capacity of the oxygen carrier II in the step (3), the drying temperature is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The method of the invention has the following advantages:
(1) the invention takes alumina with novel form as a carrier, and the alumina carrier comprises main alumina and rod-shaped alumina, wherein the rod-shaped alumina is distributed on the outer surface of the main alumina, and the rod-shaped alumina is crossed to form loose through pore channels, which is beneficial to being influenced by the diffusion effect of the surface pore structure, and can prevent metal elements from depositing on the outer surface of the alumina carrier to block the pore channels, so that the prepared hydrotreating catalyst has excellent permeability and higher metal capacity, and the blockage of the pore channels on the surface of the catalyst due to metal deposition is reduced, thereby not only ensuring the activity of the catalyst, but also ensuring the good stability of the catalyst, and prolonging the operation period of the device.
(2) The method for preparing the alumina carrier comprises the steps of preparing an alumina carrier intermediate by a conventional method, mixing the intermediate with ammonium bicarbonate and water, and carrying out sealing heat treatment to finally obtain the alumina carrier. During the heat treatment, the alumina reacts with the ammonium bicarbonate to form NH4Al(OH)2CO3NH on the outer surface4Al(OH)2CO3Grow outward to form a rod-shaped structure with nanometer-scale pore channelsNo rod-shaped structures are produced. External surface NH during subsequent firing4Al(OH)2CO3Decomposed to form a rod-shaped alumina structure, and NH is generated inside the pore channel4Al(OH)2CO3Carbon dioxide, ammonia and hydrothermal effect that take place to decompose the production play fine reaming effect simultaneously, make the connectivity of pore again more, pore is more even.
(3) In the process of preparing the alumina carrier, ammonium bicarbonate and water are mixed and then are subjected to sealing heat treatment, the pretreatment at a certain temperature is carried out before the sealing heat treatment, the conditions during the pretreatment are relatively mild, and NH is slowly formed on the outer surface of the alumina carrier in the 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 of the outer surface of the alumina carrier.
(4) The catalyst prepared by the method is suitable for the hydrotreating process of heavy raw oil, and is particularly suitable for serving as a hydrogenation protective agent, a demetallization agent and the like.
Drawings
Fig. 1 is an SEM image of a cut surface of the support I prepared in example 1.
Wherein the reference numbers are as follows: 1-bulk alumina, 2-rod alumina.
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. Wherein, in the present invention, wt% represents a mass fraction.
The BET method: 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 20nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the carriers of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is 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 of pore diameters above 100nm is determined by mercury intrusion.
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 300 g of pseudo-boehmite (produced by Shandong aluminum industry Co., Ltd., dry basis weight content of 65 wt%), 6g of carbon black powder and 3g of sesbania powder, uniformly mixing the materials, adding a proper amount of aqueous solution dissolved with 4.5 g of acetic acid, kneading, extruding into strips, forming, drying the formed product at 140 ℃ for 6 hours, and roasting the dried product at 750 ℃ for 5 hours to obtain a macroporous alumina carrier, wherein the macroporous alumina carrier has the following properties: the specific surface area is 189m2The pore volume is 0.86mL/g, and the pore distribution is as follows: the pore volume of pores with the diameter of less than 8nm accounts for 32 percent of the total pore volume, the pore volume of pores with the diameter of 8-20nm accounts for 41 percent of the total pore volume, the pore volume of pores with the diameter of more than 100nm accounts for 3 percent of the total pore volume, and the pore volume of pores with the diameter of more than 1000nm accounts for less than 1 percent of the total pore volume.
Weighing 100 g of the macroporous alumina carrier and 275 g of ammonium bicarbonate, adding 1050 g of distilled water into the materials, stirring for 20 minutes, transferring the mixed materials into a high-pressure kettle, sealing, heating to 85 ℃ at a speed of 10 ℃/min, keeping the temperature for 3 hours, heating to 145 ℃ at a speed of 5 ℃/min, keeping the temperature for 5.5 hours, drying the carrier at 110 ℃ for 6 hours, and roasting the dried carrier at 700 ℃ for 5 hours to obtain an alumina carrier I-1, wherein the properties of the carrier are shown in Table 1.
50 g of the alumina carrier is weighed and added with 100ml of Mo-Ni-P solution (MoO in impregnating solution)3Concentration of 8.2g/100ml, NiO concentration of 2.65g/100 ml) for 2 hours, filtering off the excess solution, drying at 120 ℃ for 6 hours, and then roasting at 500 ℃ for 5 hours.
The catalyst was placed in a spray-dip tumbler and 5.3ml of Mo-Ni-P solution (MoO in the dip solution)3Concentration of 1.45g/100ml and NiO concentration of 0.47g/100 ml), drying the impregnated materials at 120 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain a hydrotreating catalyst C1, wherein the content of molybdenum oxide and nickel oxide in the catalyst are respectively 9.31wt% and 3.06 wt%.
Example 2
The same as example 1 except that the amount of ammonium hydrogencarbonate added was 365 g and the amount of distilled water added was 980 g. The sealing pretreatment temperature is 75 ℃, the treatment time is 4 hours, the heat treatment temperature is 135 ℃, and the treatment time is 6.5 hours, so that the alumina carrier I-2 is prepared, and the properties of the carrier are shown in Table 1. MoO in active metal impregnation liquid I3The concentration was 7.8g/100ml and the NiO concentration was 2.45 g/100 ml. MoO in active metal impregnation liquid II3The concentration is 1.15g/100ml, the NiO concentration is 0.52g/100ml, the dosage of the active metal impregnation liquid II is 4.3ml, and the hydrodemetallization catalyst C2 is prepared, wherein the content of molybdenum oxide in the catalyst is 8.24wt%, and the content of nickel oxide in the catalyst is 2.98 wt%.
Example 3
The same as example 1 except that the amount of ammonium hydrogencarbonate added was 455 g and the amount of distilled water added was 1800 g. The sealing pretreatment temperature is 80 ℃, the treatment time is 4 hours, the heat treatment temperature is 125 ℃, and the treatment time is 7.5 hours, so that the alumina carrier I-3 is prepared, wherein the properties of the carrier are shown in Table 1. MoO in active metal impregnation liquid I3The concentration was 7.3g/100ml and the NiO concentration was 3.15 g/100 ml. Activity deviceMoO in neutral metal impregnation liquid II3The concentration is 0.85g/100ml, the NiO concentration is 0.58g/100ml, the dosage of the active metal impregnation liquid II is 6.8ml, and the hydrodemetallization catalyst C3 is prepared, wherein the content of molybdenum oxide in the catalyst is 8.16wt%, and the content of nickel oxide in the catalyst is 3.41 wt%.
Example 4
The same as example 1 except that the amount of ammonium hydrogencarbonate added was 250 g and the amount of distilled water added was 950 g. The sealing pretreatment temperature was 70 ℃, the treatment time was 3 hours, the heat treatment temperature was 155 ℃, and the treatment time was 4.5 hours, and the alumina carrier I-4 was obtained, and the properties of the carrier are shown in table 1. MoO in active metal impregnation liquid I3The concentration was 8.5g/100ml and the NiO concentration was 2.15 g/100 ml. MoO in active metal impregnation liquid II3The concentration is 1.27g/100ml, the NiO concentration is 0.36 g/100ml, the dosage of the active metal impregnation liquid II is 7.2ml, and the hydrodemetallization catalyst C4 is prepared, wherein the content of molybdenum oxide in the catalyst is 8.63wt%, and the content of nickel oxide in the catalyst is 2.54 wt%.
Example 5
In the same way as example 1, except that no pretreatment process is performed before the heat treatment, the alumina carrier and ammonium bicarbonate are added into distilled water and stirred for 20 minutes, the mixture is transferred into a high-pressure kettle and sealed, and then the temperature is raised to 145 ℃ at the speed of 10 ℃/min and kept constant for 5.5 hours, so that the alumina carrier I-5 is prepared, and the properties of the carrier are shown in Table 1. The molybdenum oxide content in the catalyst was 9.28wt%, and the nickel oxide content was 3.14 wt%.
Comparative example 1
In the same way as example 1, except that only the alumina carrier was added to distilled water for sealing heat treatment, ammonium bicarbonate was not added, and ammonium bicarbonate of the same mass was added during the molding of the macroporous alumina carrier, comparative alumina carrier S1 was obtained, the nature of the carrier is shown in table 1, the molybdenum oxide content in the catalyst was 9.32wt%, and the nickel oxide content was 3.17 wt%.
Comparative example 2
A comparative alumina support S2 was prepared as in example 1 except that ammonium bicarbonate was replaced by ammonium carbonate of the same mass, the properties of the support are shown in Table 1, and the catalyst contained 9.35wt% molybdenum oxide and 3.08wt% nickel oxide.
Comparative example 3
The same as example 1 except that the same amount of the active metal impregnation liquid II was added during kneading and molding of the alumina carrier, the properties of the comparative carrier S3 are shown in Table 1, and the content of molybdenum oxide and nickel oxide in the catalyst was 9.19wt% and 3.22 wt%.
Comparative example 4
The same as example 1, except that the same amount of active metal was loaded on the alumina carrier by one-step impregnation, the properties of the comparative carrier S4 are shown in Table 1, and the content of molybdenum oxide and nickel oxide in the catalyst is 9.25wt% and 3.24 wt%.
Comparative example 5
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 220 ℃.
Comparative example 6
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 80 ℃.
The alumina carriers prepared in the examples 1 to 5 and the comparative examples 3 and 4 comprise main alumina and rod-shaped alumina, wherein at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina carrier, and the rod-shaped alumina has the length of 1 to 12 mu m and the diameter of 100-300 nm. The alumina carrier prepared in comparative examples 1, 2, 5 and 6 has no alumina with a rod-like structure on the surface.
TABLE 1 Properties of the alumina Supports
TABLE 1 (continuous) alumina Supports Properties
Evaluation of catalytic performance:
the hydrodemetallization catalyst (C1-C9) prepared above was evaluated for its catalytic performance by the following method:
the vacuum residue listed in Table 2 was used as a raw material, and the catalytic performance of C1-C8 was evaluated on a fixed bed residue hydrogenation reaction apparatus,the catalyst has a length of 2-3mm, a reaction temperature of 380 deg.C, a hydrogen partial pressure of 13MPa, and a liquid hourly space velocity of 1.0 hr-1The volume ratio of hydrogen to oil was 1000, the content of each impurity in the produced oil was measured after 2000 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
As can be seen from the data in Table 3, compared with the comparative alumina carrier, the catalyst prepared by using the alumina of the invention as the carrier has higher hydrodemetallization activity and stability.
Claims (5)
1. A preparation method of a hydrotreating catalyst is characterized by comprising the following steps: (1) mixing an alumina carrier, ammonium bicarbonate and water, then carrying out sealing heat treatment, and drying and roasting the heat-treated material to obtain a carrier I; the carrier I is an alumina carrier with a rod-shaped structure growing on the surface; (2) supersaturating a hydrogenation active component impregnation solution I to impregnate a carrier I, and then drying and roasting to obtain a carrier II; (3) unsaturated spraying the hydrogenation active component impregnation liquid II to impregnate the carrier II, and then drying and roasting to prepare a hydrogenation catalyst; the sealing heat treatment conditions in the step (1) are as follows: the temperature is 120-; the carrier I is an alumina carrier with a surface growing rod-shaped structure, and comprises main alumina and rod-shaped alumina, wherein at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina carrier, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm; the coverage rate of the rod-shaped alumina on the outer surface of the main alumina of the carrier I70% -95%, wherein the coverage rate refers to the percentage of the surface occupied by the rod-shaped alumina on the outer surface of the main alumina to the outer surface of the main alumina; the carrier I has the following properties: the specific surface area is 140-250m2The pore volume is 0.8-1.0mL/g, the diameters of several pores are 10-50nm, 100-500nm and 500-1000nm, and the crushing strength is 110-140N/cm; the property of the alumina carrier in the step (1) is as follows: the specific surface area is 150-230m2The pore volume is 0.7-0.9mL/g, and the average pore diameter is 10-30 nm.
2. The method of claim 1, wherein: the particle size of the alumina carrier in the step (1) is 0.5-8.0 mm.
3. The method of claim 1, wherein: in the step (1), the ammonium bicarbonate and the alumina carrier are Al2O3The mass ratio of the water to the water is 2.5-5: 1: 5-20.
4. The method of claim 1, wherein: the step (1) is to carry out sealing pretreatment before sealing heat treatment, wherein the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, 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.
5. The method of claim 1, wherein: the hydrogenation active component impregnation liquid is a solution containing VIB and/or VIII group metals, the VIB group metals are molybdenum and/or tungsten, and the VIII group metals are cobalt and/or nickel; the content of VIB group metals in the hydrogenation active component impregnating solution I in the step (2) is 6.5-15.0g/100mL calculated by metal oxides, and the content of VIII group metals is 1.5-3.5g/100mL calculated by metal oxides; in the hydrogenation active component impregnating solution II in the step (3), the content of VIB group metals is 0.8-1.5g/100mL calculated by oxides, the content of VIII group metals is 0.3-0.6g/100mL calculated by oxides, and the dosage of the hydrogenation active component impregnating solution II is 8-15% of the water absorption capacity of the carrier II.
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