CN117000255A - Hydrodemetallization catalyst and preparation method thereof - Google Patents
Hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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- CN117000255A CN117000255A CN202210456984.9A CN202210456984A CN117000255A CN 117000255 A CN117000255 A CN 117000255A CN 202210456984 A CN202210456984 A CN 202210456984A CN 117000255 A CN117000255 A CN 117000255A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims 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 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 52
- 238000001035 drying Methods 0.000 claims description 43
- 239000002002 slurry Substances 0.000 claims description 39
- 238000005470 impregnation Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 24
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 24
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 24
- 239000001099 ammonium carbonate Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229920003169 water-soluble polymer Polymers 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003921 oil Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- -1 VIB metal compound Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- 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
- 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
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J37/0205—Impregnation in several steps
-
- 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
-
- 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
- C10G2300/205—Metal content
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hydrodemetallization catalyst and a preparation method thereof. The catalyst comprises a carrier component and a second active component, wherein the second active component comprises molybdenum and a VIII group metal, the carrier component comprises alumina, carbon and a first active component, and the first active component comprises molybdenum and a VIII group metal; the mass ratio of alumina to carbon in the carrier is 5.5-24.5; wherein, the content ratio of tetrahedral molybdenum and octahedral molybdenum in the catalyst is 0.13-0.25 based on Mo atom. The catalyst is applied to the residual oil hydrodemetallization catalyst, and the activity and stability of the catalyst are obviously improved.
Description
Technical Field
The invention relates to a hydrodemetallization catalyst, in particular to a hydrodemetallization catalyst applicable to a heavy oil, especially residual oil hydrotreatment process and a preparation method thereof.
Background
In recent years, the trend of heavy and poor quality of crude oil is increasing, but the market demand for light oil is increasing. This leaves the hydrogenation technology as an important treatment route for heavy oils with challenges. As the core of the hydrogenation technology, the preparation technology and the performance of the catalyst play important roles in deep hydrogenation of heavy oil. For the hydrogenation of residuum, the hydrodemetallization reaction of residuum is one of important chemical reactions in the hydrotreating process of residuum, and under the action of catalyst, various metal compounds and H 2 The S reaction produces metal sulfides which are subsequently deposited on the catalyst and thus removed. The existence state of the active metal on the catalyst carrier can play an important role in the activity stability of the catalyst.
CN102441399a discloses a preparation method of hydrodemetallization catalyst, which prepares a group VIB metal compound and/or a group VIII metal compound into ammonia solution or aqueous solution, then impregnates an alumina carrier, and finally prepares the final catalyst through drying and roasting. CN1289640a discloses a preparation method of supported hydrodemetallization catalyst, which adopts macroporous alumina carrier, and sprays ammonia solution or aqueous solution of active metal on the carrier in a spray-dipping roller pot, the method omits normal temperature drying process of the carrier after dipping, the sprayed carrier is directly placed in a roasting furnace with the temperature of 300-450 ℃ for roasting, then gradually rises to 460-550 ℃, and the temperature is kept constant for 1-5 hours under the air condition. CN103785400a discloses a preparation method of a high-activity residual oil hydrodemetallization catalyst, which comprises the steps of impregnating an alumina carrier with a polyalcohol and/or monosaccharide aqueous solution, carrying out hydrothermal carbonization treatment in a sealed container after the impregnation is finished, then loading active metal components Mo and Ni on the carrier, and finally roasting the alumina loaded with the active components in a nitrogen atmosphere, and then roasting in an air atmosphere to obtain the residual oil hydrodemetallization catalyst.
The activity and stability of the hydrodemetallization catalyst prepared by the method are still to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrodemetallization catalyst and a preparation method thereof. When the catalyst is used for hydrogenation demetalization reaction of residual oil, the activity and stability of hydrogenation reaction can be obviously improved.
The first aspect of the present invention provides a hydrodemetallization catalyst comprising a support component and a second active component, the second active component comprising molybdenum and a group VIII metal, the support component comprising alumina, carbon and a first active component, the first active component comprising molybdenum and a group VIII metal; the mass ratio of alumina to carbon in the carrier is 5.5-24.5, preferably 8.0-13.5; wherein, in the catalyst, the content ratio of tetrahedral molybdenum and octahedral molybdenum is 0.13-0.25 based on Mo atom.
In the present invention, the group VIII metal in the first active component is preferably nickel.
In the present invention, the second active component comprises molybdenum and a group VIII metal, preferably nickel.
In the invention, moO is based on the mass of the catalyst 3 The content of the metal oxide of the VIII family is 5.0 to 20.0 percent, and the content of the metal oxide of the VIII family is 2.0 to 6.0 percent.
In the invention, the total MoO in the catalyst 3 MoO in the first active component based on mass 3 The content of the second active component is 35.0% -65.0%, and MoO in the second active component 3 The content of (3) is 35.0-65.0%.
In the invention, the content of the VIII group metal oxide in the first active component is 35.0-65.0% and the content of the VIII group metal oxide in the second active component is 35.0-65.0% based on the mass of the total VIII group metal oxide in the catalyst.
In the invention, the specific surface area of the catalyst is 140-210 m 2 Per g, pore volume is 0.50-1.10 mL/g, and pore diameter is 13-25 nm.
In the present invention, preferably, the specific surface area of the catalyst is 165 to 200m 2 Per g, pore volume is 0.85-0.95 mL/g, and pore diameter is 17-24 nm.
In the invention, the catalyst also comprises an auxiliary component, wherein the auxiliary component is at least one selected from fluorine, phosphorus, silicon or boron, and preferably phosphorus. The content of the auxiliary agent component calculated by oxide is 1.0% -4.0% based on the mass of the catalyst.
The second aspect of the invention provides a preparation method of the hydrodemetallization catalyst, which comprises the following steps:
(1) Neutralizing the acidic aluminum salt solution with the alkaline aluminum salt solution, and aging for the first time to obtain slurry;
(2) Dividing the slurry obtained in the step (1) into slurry I and slurry II, adding a water-soluble high polymer J1 into the slurry II, respectively carrying out secondary aging on the slurry I and the slurry II, and drying to obtain a dried substance I and a dried substance II;
(3) Immersing the dried material I obtained in the step (2) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, and drying to obtain a material A;
(4) Immersing the dried material II obtained in the step (2) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, drying, impregnating the material with a first active component metal impregnating solution in an unsaturated impregnation mode, and drying to obtain a material B;
(5) Kneading, molding, drying and first roasting the material A and the material B to obtain a carrier;
(6) Impregnating the carrier obtained in the step (5) with a second active component metal impregnation liquid in a saturated impregnation mode, drying and roasting for the second time to obtain the catalyst.
In the step (1) of the invention, the acidic aluminum salt solution and the alkaline aluminum salt solution are added into a reaction kettle in a parallel flow mode.
In the step (1) of the invention, the acidic aluminum salt solution is aluminum sulfate solution, aluminum nitrate solution or aluminum chloride solutionOne or more of the following; the acidic aluminum salt solution is prepared by using Al 2 O 3 The concentration is 8g/100 mL-28 g/100mL. The alkaline aluminum salt solution is one or two of sodium metaaluminate solution and potassium metaaluminate solution; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The concentration is 10g/100 mL-50 g/100mL.
In the step (1), the temperature of the neutralization reaction is 75-120 ℃, the time is 30-150 minutes, and the pH value of the slurry is controlled to be 6.0-9.8 in the neutralization reaction process. The pH value of the slurry is regulated by controlling the adding rate of the acidic aluminum salt solution and the alkaline aluminum salt solution or adding an acid-base regulator additionally in the neutralization reaction process.
In the step (1), the primary aging temperature is 90-240 ℃, the time is 50-240 minutes, and the pH value is 9.0-10.0.
In step (2) of the present invention, after the primary aging is completed, the slurry is preferably concentrated and then subjected to secondary aging. Wherein the volume of the concentrated slurry is 30-70% of the original volume.
In the step (2) of the invention, no substance is added to the slurry I. The water-soluble high polymer J1 added into the slurry II is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, and is preferably polyethylene glycol; the viscosity of the water-soluble polymer J1 (20 ℃) is 10 to 1000 mPas, and the viscosity of the slurry II (20 ℃) is 120 to 660 mPas after the water-soluble polymer J1 is added.
In the step (2), the temperature of the secondary aging is 120-270 ℃, the time is 40-190 minutes, and the temperature of the secondary aging is 30-60 ℃ higher than the temperature of the primary aging.
In the step (2), the drying temperature is 120-180 ℃ after secondary aging, the drying time is 2-10 h, and the filtering and washing can be carried out according to a conventional known method before drying. The dry basis content of the dried material I and the dried material II obtained after drying is 30-70wt%.
In the step (3) of the invention, the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 10-20%. The sealing heat treatment temperature is 80-140 ℃, preferably 110-140 ℃ and the treatment time is 6-12 h. The drying temperature is 120-180 ℃ and the drying time is 2-10 h.
In the step (4), the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 20-30%. The sealing heat treatment temperature is 80-140 ℃, preferably 80-110 ℃, wherein the heat treatment temperature in the step (4) is 30-50 ℃ lower than the heat treatment temperature in the step (3), and the treatment time is 6-12 h. The drying temperature is 120-180 ℃ and the drying time is 2-10 h.
The mass concentration of the ammonium bicarbonate aqueous solution in the step (4) is 8-15 percent higher than that in the step (3).
In the step (4), the consumption of the metal impregnating solution of the first active component accounts for 10-40% of the saturated water absorption of the impregnated material.
In the step (4) of the invention, the first active component metal impregnating solution is an impregnating solution containing Mo and a group VIII metal (preferably Ni), wherein the active metal component molybdenum is one or two of molybdenum oxide and ammonium heptamolybdate, the nickel is one or two of basic nickel carbonate and nickel nitrate, and MoO in the first active component metal impregnating solution 3 And the group VIII metal oxide content is 30.0 to 80.0g/100ml,5.0 to 40.0g/100ml, respectively. Wherein MoO introduced into the catalyst from the first active component metal impregnation liquid 3 In the amount of total MoO in the catalyst 3 35% -65% of load capacity; the amount of the group VIII metal oxide introduced into the catalyst from the first active component metal impregnation solution is 35% to 65% of the total group VIII metal oxide loading in the catalyst.
In the step (4) of the invention, at least one auxiliary agent containing fluorine, phosphorus, silicon or boron can be introduced into the first active component metal impregnation liquid, and the addition amount of the auxiliary agent (calculated by oxide) is 18-28% of the total mass of molybdenum oxide in the first active component metal impregnation liquid, preferably 20-25%.
In the step (4) of the present invention, it is preferable that the first active ingredient metal impregnation liquid further contains a water-soluble polymer J2. The water-soluble polymer J2 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like. The viscosity of the water-soluble polymer J2 is 10 to 1000 mPas, and the viscosity of the slurry (20 ℃) after the water-soluble polymer J2 is added is 150 to 800 mPas.
In the step (4), the dipping adopts a spray dipping method, and the spray dipping time is 15-35 min.
In the step (4), after the impregnation is finished, the material is dried for 2 to 8 hours at the temperature of 20 to 40 ℃ and then dried for 2 to 12 hours at the temperature of 120 to 200 ℃.
In the step (5), the material A accounts for 15-45% of the total mass of the material A and the material B. In the forming process, one or more conventional forming aids such as a peptizing agent, an extrusion aid and the like can be added according to the need, wherein the peptizing agent is one or more of nitric acid, sulfuric acid and oxalic acid, and the extrusion aid is one or more of sesbania powder, cellulose and resin.
In the step (5), the drying temperature is 20-200 ℃ and the drying time is 2-12 h.
In step (5) of the present invention, the first firing temperature is 500 to 750 ℃, the firing time is 2 to 6 hours, and the firing atmosphere is an inert atmosphere (such as nitrogen) or steam, preferably steam.
In the step (6) of the invention, the second active component metal impregnation liquid contains an impregnation liquid of Mo and a metal of a group VIII (preferably Ni), wherein the active metal component molybdenum is one or two of molybdenum oxide and ammonium heptamolybdate, and the nickel is one or two of basic nickel carbonate and nickel nitrate. Wherein MoO introduced into the catalyst from the second active component metal impregnation liquid 3 In the amount of total MoO in the catalyst 3 35% -65% of load capacity; the amount of the group VIII metal oxide introduced into the catalyst from the second active component metal impregnation solution is 35% to 65% of the total group VIII metal oxide loading in the catalyst.
In the step (6) of the present invention, it is preferable that the second active ingredient metal impregnation liquid further contains a water-soluble polymer J3. The water-soluble polymer J3 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like. The viscosity of the water-soluble polymer J3 (20 ℃) is 10 to 1000 mPas, and the viscosity of the slurry after the water-soluble polymer J3 is added (20 ℃) is 150 to 800 mPas.
In the step (6), the dipping adopts a spray dipping method, and the spray dipping time is 15-35 min.
In the step (6), the drying temperature is 120-200 ℃ and the drying time is 2-12 h.
In step (6) of the present invention, the second firing temperature is 350 to 450 ℃ and the firing time is 2 to 6 hours, and the firing atmosphere is an inert atmosphere (such as nitrogen) or steam, preferably steam.
Compared with the prior art, the invention has the following beneficial effects:
for hydrodemetallization catalysts, good pore channel structure and reasonable active metal distribution on the catalyst are of great significance for the exertion of the catalytic performance of the catalyst. Whereas the reduction temperature of the tetrahedral Mo species is greater than that of the octahedral Mo species, the presence of tetrahedral Mo has an adverse effect on weakening the interactions between the support and the metal, thus affecting the catalyst activity and stability. The inventor finds that, through a great deal of researches, firstly, the carrier is optimized, the slurry obtained after the neutralization reaction is aged for two sections, the obtained slurry is respectively treated without adding water-soluble high polymer and before the secondary aging, and the secondary aging is performed at a higher temperature, so that porous materials with proper specific surface area and different pore size distribution, namely a dried material I and a dried material II, can be obtained; and then immersing the dried material I in an ammonium bicarbonate aqueous solution and then carrying out sealing heat treatment to obtain a material A, immersing the dried material II in the ammonium bicarbonate aqueous solution, then carrying out sealing heat treatment, and simultaneously spraying and immersing the first active component metal impregnating solution on the dried material II subjected to ammonium bicarbonate treatment in an unsaturated impregnation mode to obtain a material B. Kneading and molding the material A and the material B, and drying and roasting for the first time to obtain a carrier; finally, the second active component metal impregnating solution is loaded on the obtained carrier in a saturated impregnation mode, and then the second roasting is carried out, so that the species proportion of tetrahedral molybdenum and octahedral molybdenum in the catalyst is proper. In the preparation process of the carrier, the drying I and the drying II are respectively subjected to ammonium bicarbonate heat treatment, and a macroporous structure can be formed in the subsequent roasting process, so that on one hand, the pore channel structure of the carrier is favorably regulated, and a proper pore channel structure is provided for the diffusion of macromolecules in residual oil; on the other hand, more possible places can be provided for the deposition of metal in the residual oil, so that the metal capacity of the catalyst is improved. Preferably, the metal impregnation solutions of the first and second active components are each added with a water-soluble polymer, which on the one hand promotes the dispersion of the active metal and on the other hand allows the acidity of the catalyst to be appropriately adjusted. The method of the invention improves the activity and stability of the residual oil hydrodemetallization catalyst obviously through the comprehensive coordination of the steps.
Drawings
FIG. 1 is a Raman spectrum of the catalyst surface obtained in example 1;
FIG. 2 is a Raman spectrum of the catalyst surface obtained in comparative example 1;
FIG. 3 is a Raman spectrum of the catalyst surface obtained in comparative example 2;
FIG. 4 is a Raman spectrum of the catalyst surface obtained in comparative example 3.
Detailed Description
In the invention, a Thermo Scientific company DXR Microscope type DXR microscopic Raman spectrometer is adopted to carry out Raman spectrum characterization of the catalyst. Wherein at 930cm -1 The nearby peak is tetrahedral molybdenum peak, at 960cm -1 The nearby peaks are those of octahedral molybdenum, and the contents of tetrahedral molybdenum and octahedral molybdenum are calculated as the area at the same base line.
In the invention, the pore Structure (SVD) and specific surface area of the catalyst are characterized by using an ASAP-2420 physical adsorption instrument of Michael company.
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited to the following examples.
Example 1
1.5L of an aqueous solution of aluminum sulfate (as Al 2 O 3 The measured concentration is 10.0g/100mL, the initial temperature is 75 ℃, and 1L of sodium metaaluminate aqueous solution (Al is used) is introduced into a reaction kettle provided with a 5L pure water band stirrer and a heating sleeve from the upper part 2 O 3 The concentration is 28.0g/100mL, the initial temperature is 110 ℃ from the bottom of the kettleIntroducing the reaction kettle into the part, and controlling the neutralization reaction temperature at 105 ℃; continuously adding an aluminum sulfate solution and a sodium metaaluminate solution, controlling the pH value to be 8.5, and reacting for 60 minutes; after the parallel flow is finished, carrying out primary aging, wherein the aging temperature is 140 ℃, the aging time is 120 minutes, and the aging pH value is 9.3; concentrating until the volume of the slurry reaches 5L after the primary aging is finished, uniformly dividing the slurry into two parts, namely slurry I and slurry II, adding 25g of polyvinyl alcohol (with the viscosity of 30 mPa.s) into the slurry II, adding the polyvinyl alcohol, wherein the viscosity of the slurry (20 ℃) is 260 mPa.s, and the slurry I does not undergo any treatment, then heating the slurry I and the slurry II to 170 ℃, carrying out secondary aging for 120 minutes, washing and drying to obtain a dried product I and a dried product II with the dry weight of 50wt% respectively;
100g of dried matter I is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 18%, and after being evenly mixed, the dried matter I is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 135 ℃, and the treatment time is 6 hours. And then carrying out suction filtration on the obtained sample, and drying at 175 ℃ for 4 hours to obtain a material A. Similarly, 100g of dried matter II is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 26%, and after being uniformly mixed, the dried matter II is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 85 ℃ and the treatment time is 10 hours. The sample obtained is then suction filtered, dried at 145℃for 4 hours and then impregnated with the first active ingredient metal impregnation (MoO 3 The content of NiO is 66.1g/100ml, the content of NiO is 15.1g/100ml, the addition amount of P (calculated as oxide) in the auxiliary phosphoric acid is 23.6% of the total mass of molybdenum oxide in the impregnating solution), the dried matter II after spray-dipping heat treatment (the use amount of the first active component metal impregnating solution is 22% of the saturated water absorption amount of the dried matter II), and the polyacrylamide (viscosity is 950 mPa.s) is added into the first active component metal impregnating solution, the viscosity is 650 mPa.s after the addition, wherein MoO introduced into the catalyst by the first active component metal impregnating solution 3 In the amount of total MoO in the catalyst 3 40% of the loading; the amount of NiO introduced into the catalyst by the metal impregnation liquid of the first active component is 40% of the total NiO loading in the catalyst, the spraying and impregnating time is controlled within 30min, then the catalyst is kept stand and dried for 2h at the room temperature of 25 ℃, and then the obtained sample is dried at 120 DEG CDrying for 6 hours to obtain a material B;
kneading the material A and the material B according to the mass ratio of 1:4, and adding 3.0wt% of acetic acid and 2.0wt% of sesbania powder in the molding process. The molded sample was dried at 120℃for 4 hours. And then roasting the carrier at 750 ℃ for 3 hours in the steam atmosphere to obtain the catalyst carrier containing partial active metals.
Weighing 200g of catalyst carrier containing partial active metal, carrying out secondary impregnation on the second active component metal impregnation liquid in a saturated impregnation mode, adding polyacrylamide (with the viscosity of 950 mPas) into the second active component metal impregnation liquid, and adding the polyacrylamide into the second active component metal impregnation liquid to obtain a catalyst carrier with the viscosity of 350 mPas, wherein MoO introduced into the catalyst by the second active component metal impregnation liquid 3 In the amount of total MoO in the catalyst 3 60% of the load; the amount of NiO introduced into the catalyst by the second active component metal impregnation liquid is 60 percent of the total NiO loading in the catalyst, the spray dipping time is controlled within 30 minutes, then the catalyst is dried at 120 ℃ for 6 hours, and is roasted at 350 ℃ for 5 hours, wherein the heating rate in the roasting process is 3 ℃/min, and the hydrodemetallization catalyst CAT-1 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 2
This example differs from example 1 in that the initial temperature of the aqueous sodium metaaluminate solution added is 100℃and 50g of polyvinyl alcohol (viscosity 30 mPas) is added to the slurry II after primary aging and the viscosity of the slurry after addition of polyvinyl alcohol (20 ℃) is 280 mPas;
100g of dried matter I is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 16%, and after being uniformly mixed, the dried matter I is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 125 ℃, and the treatment time is 8 hours. And then carrying out suction filtration on the obtained sample, and drying at 165 ℃ for 6 hours to obtain a material A. Similarly, 100g of dried matter II is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 26%, and after being uniformly mixed, the dried matter II is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 95 ℃ and the treatment time is 8 hours. The sample obtained was then suction filtered and dried at 155℃for 6h, and then the heat treated dried product II (same as in example 1) was spray-immersed with the first active ingredient metal impregnation solution to give material B. Kneading the material A and the material B according to the mass ratio of 3:8, and forming. In the first roasting process, the temperature is raised to 700 ℃ at a heating rate of 3 ℃/min for roasting for 4 hours; in the second roasting process, the temperature is raised to 400 ℃ at a heating rate of 3 ℃/min for roasting for 4 hours, and the hydrodemetallization catalyst CAT-2 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 3
The difference between this example and example 1 is that 100g of the dried product I is taken and placed in 300g of an aqueous solution of ammonium bicarbonate with a mass percentage concentration range of 14%, and after being mixed uniformly, the mixture is transferred into an autoclave for sealing heat treatment at 135 ℃ for 10 hours. And then carrying out suction filtration on the obtained sample, and drying at 155 ℃ for 8 hours to obtain a material A. Similarly, 100g of dried matter II is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 26%, and after being uniformly mixed, the dried matter II is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 105 ℃, and the treatment time is 6 hours. The sample obtained was then suction filtered and dried at 165℃for 8h, and then the heat-treated dried product II (same as in example 1) was spray-immersed with the first active ingredient metal impregnation liquid, giving material B. Kneading the material A and the material B according to the mass ratio of 1:2, and forming. In the first roasting process, the temperature is raised to 650 ℃ at a heating rate of 3 ℃/min for roasting for 5 hours; in the second roasting process, the temperature is raised to 450 ℃ at a heating rate of 3 ℃/min for roasting for 3 hours, and the hydrodemetallization catalyst CAT-3 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 4
The difference between this example and example 1 is that 100g of the dried product I is taken and placed in 300g of an aqueous solution of ammonium bicarbonate with a mass percentage concentration range of 12%, and after being mixed uniformly, the mixture is transferred into an autoclave for sealing heat treatment at 140 ℃ for 12 hours. And then carrying out suction filtration on the obtained sample, and drying at 145 ℃ for 10 hours to obtain a material A. Similarly, 100g of dried matter II is taken and placed in 300g of ammonium bicarbonate aqueous solution with the mass percentage concentration range of 26%, and after being uniformly mixed, the dried matter II is transferred into an autoclave for sealing heat treatment, wherein the treatment temperature is 110 ℃, and the treatment time is 6 hours. Then willThe obtained sample was suction-filtered, dried at 175℃for 10 hours, and then the heat-treated dried product II (same as in example 1) was spray-immersed in the first active ingredient metal impregnation liquid to obtain a material B. Except for MoO introduced into the catalyst from the first active component metal impregnation liquid 3 In the amount of total MoO in the catalyst 3 30% of the load; the amount of NiO introduced into the catalyst by the first active component metal impregnation liquid was 30% of the total NiO loading in the catalyst. In the first roasting process, the temperature is raised to 600 ℃ at a heating rate of 3 ℃/min for 6 hours; in the second roasting process, the temperature is raised to 500 ℃ at a heating rate of 3 ℃/min for roasting for 3 hours, and the hydrodemetallization catalyst CAT-4 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Comparative example 1
Compared with example 1, the hydrodemetallization catalyst dCAT-1 was prepared without immersing the dried material I and the dried material II in an aqueous ammonium bicarbonate solution and then performing a sealing heat treatment. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 2
Compared with example 1, the method is characterized in that the active metal impregnating solution containing the same amount of metal is directly kneaded and molded with a dried substance I and a dried substance II (the treatment process in example 1), so as to prepare the hydrodemetallization catalyst dCAT-2. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 3
Compared with example 1, the difference is that the concentration of ammonium bicarbonate solution for treating the dried material I and the dried material II is 12%, the sealing heat treatment temperature in an autoclave is 135 ℃, the treatment time is 6 hours, the drying temperature after suction filtration is 175 ℃, and the drying time is 4 hours. The hydrodemetallization catalyst dCAT-3 is prepared. The physicochemical properties of this catalyst are shown in Table 1.
TABLE 1 physicochemical Properties of hydrogenation catalysts
Evaluation test
Hydrodemetallizing the residue obtained as described aboveThe catalysts, examples 1 to 4 and comparative examples 1 to 3, were subjected to activity stability tests in a 200ml fixed bed hydrogenation test apparatus under the following reaction conditions: the reaction temperature is 390 ℃, the hydrogen partial pressure is 15.0MPa, and the liquid hourly space velocity is 1.0h -1 The hydrogen oil volume ratio was 800, the demetallization rate of each catalyst during the reaction for 1200h is shown in table 3, and the raw oil properties are shown in table 2.
TABLE 2 oil Properties of raw materials
| Nature of raw oil | Middle eastern residuum |
| S，wt％ | 3.3 |
| Ni，μg/g | 30.6 |
| V，μg/g | 64.5 |
Table 3 test results for hydrodemetallization catalysts of various examples
As can be seen from tables 1, 2 and 3, the hydrodemetallization catalyst prepared by the method has higher specific surface area and pore volume, higher reactivity and stability, and can well satisfy the hydrodemetallization process of heavy oil, especially residual oil.
Claims (16)
1. A hydrodemetallization catalyst comprising a support component and a second active component, the second active component comprising molybdenum and a group VIII metal, the support component comprising alumina, carbon and a first active component comprising molybdenum and a group VIII metal; the mass ratio of alumina to carbon in the carrier is 5.5-24.5, preferably 8.0-13.5; wherein, in the catalyst, the content ratio of tetrahedral molybdenum and octahedral molybdenum is 0.13-0.25 based on Mo atom.
2. The catalyst of claim 1 wherein the group VIII metal in the first and second active components is nickel.
3. The catalyst according to claim 1, wherein MoO is calculated on the basis of the catalyst mass 3 The content of the metal oxide of the VIII family is 5.0 to 20.0 percent, and the content of the metal oxide of the VIII family is 2.0 to 6.0 percent.
4. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 140-210 m 2 Per gram, pore volume of 0.50-1.10 mL/g, pore diameter of 13-25 nm, preferably, specific surface area of 165-200 m 2 Per g, pore volume is 0.85-0.95 mL/g, and pore diameter is 17-24 nm.
5. Catalyst according to claim 1, characterized in that the catalyst further comprises an auxiliary component, which is at least one selected from fluorine, phosphorus, silicon or boron, preferably phosphorus, and the content of the auxiliary component is 1.0-4.0% in terms of oxide based on the mass of the catalyst.
6. The method for preparing the hydrodemetallization catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) Neutralizing the acidic aluminum salt solution with the alkaline aluminum salt solution, and aging for the first time to obtain slurry;
(2) Dividing the slurry obtained in the step (1) into slurry I and slurry II, adding a water-soluble high polymer J1 into the slurry II, respectively carrying out secondary aging on the slurry I and the slurry II, and drying to obtain a dried substance I and a dried substance II;
(3) Immersing the dried material I obtained in the step (2) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, and drying to obtain a material A;
(4) Immersing the dried material II obtained in the step (2) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, drying, impregnating the material with a first active component metal impregnating solution in an unsaturated impregnation mode, and drying to obtain a material B;
(5) Kneading, molding, drying and first roasting the material A and the material B to obtain a carrier;
(6) Impregnating the carrier obtained in the step (5) with a second active component metal impregnation liquid in a saturated impregnation mode, drying and roasting for the second time to obtain the catalyst.
7. The method of claim 6, wherein in step (1), the acidic aluminum salt solution and the basic aluminum salt solution are subjected to a cocurrent neutralization reaction; the acidic aluminum salt solution is prepared by using Al 2 O 3 The calculated concentration is 8g/100 mL-28 g/100mL; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The calculated concentration is 10g/100 mL-50 g/100mL; preferably, in the step (1), the temperature of the neutralization reaction is 75-120 ℃, the time is 30-150 minutes, and the pH value of the slurry is controlled to be 6.0-9.8 in the neutralization reaction process.
8. The method according to claim 6, wherein in the step (2), the primary aging is carried out at a temperature of 90 to 240 ℃ for 50 to 240 minutes and at a pH of 9.0 to 10.0; and/or in the step (2), the temperature of the secondary aging is 120-270 ℃, the time is 40-190 minutes, and the temperature of the secondary aging is 30-60 ℃ higher than the temperature of the primary aging.
9. The preparation method according to claim 6, wherein in the step (2), the water-soluble polymer J1 added to the slurry II is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, preferably polyethylene glycol; the viscosity of the water-soluble polymer J1 is 10 to 1000 mPas, and the viscosity of the slurry after the water-soluble polymer J1 is added is 120 to 660 mPas.
10. The process according to claim 6, wherein in the step (2), the drying temperature is 120 to 180℃and the drying time is 2 to 10 hours, and the dry matter I and the dry matter II obtained after the drying have a dry matter content of 30 to 70% by weight.
11. The method according to claim 6, wherein in the step (3), the mass concentration of the ammonium bicarbonate aqueous solution is 10% to 20%; and/or in the step (4), the mass concentration of the ammonium bicarbonate aqueous solution is 20-30%, and the mass concentration of the ammonium bicarbonate aqueous solution in the step (4) is 8-15% higher than that in the step (3).
12. The method according to claim 6, wherein in step (3), the sealing heat treatment temperature is 80 to 140 ℃, preferably 110 to 140 ℃, the treatment time is 6 to 12 hours, the drying temperature is 120 to 180 ℃, and the drying time is 2 to 10 hours; and/or in the step (4), the sealing heat treatment temperature is 80-140 ℃, preferably 80-110 ℃, the treatment time is 6-12 h, the drying temperature is 120-180 ℃ and the drying time is 2-10 h; wherein the heat treatment temperature in the step (4) is 30-50 ℃ lower than the heat treatment temperature in the step (3).
13. The method according to claim 6, wherein in the step (4), at least one auxiliary agent containing fluorine, phosphorus, silicon or boron is introduced into the first active component metal impregnation liquid, and the addition amount of the auxiliary agent calculated by oxide is 18% -28%, preferably 20% -25% of the total mass of the molybdenum oxide in the first active component metal impregnation liquid.
14. The method of claim 6, wherein in step (4), the first active ingredient metal impregnation liquid is used in an amount of 10% to 40% of the saturated water absorption of the impregnated material.
15. The method according to claim 6, wherein in the step (5), the material A accounts for 15% -45% of the total mass of the material A and the material B.
16. The method according to claim 6, wherein in step (5), the first firing temperature is 500 to 750 ℃, the firing time is 2 to 6 hours, and the firing atmosphere is an inert atmosphere or steam, preferably steam; and/or in the step (6), the second roasting temperature is 350-450 ℃, the roasting time is 2-6 h, and the roasting atmosphere is inert atmosphere or steam, preferably steam.
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