CN116020476B - Hydrogenation pretreatment catalyst and preparation method and application thereof - Google Patents
Hydrogenation pretreatment catalyst and preparation method and application thereof Download PDFInfo
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- CN116020476B CN116020476B CN202111242774.1A CN202111242774A CN116020476B CN 116020476 B CN116020476 B CN 116020476B CN 202111242774 A CN202111242774 A CN 202111242774A CN 116020476 B CN116020476 B CN 116020476B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- 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 66
- 239000002253 acid Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- -1 VIB metal oxide Chemical class 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 42
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 235000005770 birds nest Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 235000005765 wild carrot Nutrition 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 241000219793 Trifolium Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100400452 Caenorhabditis elegans map-2 gene Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WDEOTCWPXLWTRP-UHFFFAOYSA-N [C+4].[O-2].[Al+3] Chemical compound [C+4].[O-2].[Al+3] WDEOTCWPXLWTRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 101150064138 MAP1 gene Proteins 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 101150108611 dct-1 gene Proteins 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
Abstract
The invention discloses a hydrogenation pretreatment catalyst and a preparation method and application thereof, wherein the catalyst takes carbon-containing alumina as a carrier, takes VIB metal oxide and/or VIII metal oxide as active components, and takes the weight of the final hydrogenation pretreatment catalyst as a reference, the mass content of carbon is 0.10-1.90 wt%, preferably 0.12-1.70 wt%; the acid quantity at the temperature of more than 300 ℃ is 0.160 mmol/g-0.205 mmol/g. The preparation method comprises the following steps: firstly, introducing a VIB metal and/or a VIII metal component into a carbon-containing alumina carrier; and then drying and roasting to obtain the final hydrogenation pretreatment catalyst. The catalyst has proper acid distribution, can obviously improve the synergistic effect of active metal and an acid center, and improves the activity stability of the catalyst.
Description
Technical Field
The invention relates to a hydrogenation pretreatment catalyst and a preparation method and application thereof, in particular to a high-activity hydrogenation pretreatment catalyst suitable for treating straight-run oil and a preparation method and application thereof.
Background
Along with the gradual deterioration of the quality of crude oil processed in China, a refinery gradually starts to process some heavy raw oil, the feeding of a subsequent hydrogenation device also becomes heavy, and the impurity content is also increased. As an important technology for directly converting inferior raw oil into acceptable fuel products and chemical raw materials, the processing direction is also moving toward heavier raw oil. Processing heavy feedstock oil will place higher demands on the activity of the hydroprocessed catalyst: on the one hand, the hydrotreating catalyst should have a larger pore size so as to ensure that large-size molecules can be efficiently transferred to the active center; on the other hand, the active center of the catalyst should have stronger hydrogenation and hydrogenolysis properties, and can rapidly complete hydrogenation and hydrogenolysis processes. The reaction temperature of the bed where the hydrotreating catalyst is located shows a gradient change, and thus, the catalyst is required to have different metal centers and acid centers. The traditional catalyst preparation method is that a metal solution is directly immersed on a carrier, and metal in the catalyst obtained by roasting can interact with the carrier to form spinel, so that the utilization rate of the metal is reduced; meanwhile, strong acid in the catalyst is reduced in the process of loading metal, so that the activity of the catalyst is gradually deteriorated. Therefore, how to improve the preparation process of the catalyst, not only can fully disperse metal, but also can selectively and properly reserve the acid center in the carrier, so that the acid center and the hydrogenation center are reasonably matched, and the guarantee of the activity stability of the catalyst becomes a key for preparing the hydrogenation pretreatment catalyst.
Chinese patent CN 103785404A discloses a preparation method of a hydrotreating catalyst, which is mainly to pre-impregnate an alumina carrier with an ammonium salt solution, and then transfer the pre-impregnated alumina carrier into a closed container for heat treatment, so as to improve the surface performance of the alumina carrier, improve the dispersity of metal components on the surface of the body, and further greatly improve the denitrification performance of the catalyst.
Chinese patent CN 107442126a discloses a preparation method of a hydrotreating catalyst, in which water-soluble silicone oil and carbon precursor are introduced into alumina carrier in sequence or simultaneously to improve the properties of the carrier. The introduced carbonic acid can disperse active metal centers, and the introduced silicon and other auxiliary agents can cooperatively form acidic centers with proper polyacid, so that the synergistic effect of the metal and the acidic centers can be regulated, and the denitrification performance of the catalyst is further improved.
Chinese patent CN105833879a discloses a hydrotreating catalyst and a preparation method thereof, mainly adopting a combination of complexing agent roasting-drying. Introducing complexing agent into the prepared alumina carrier, and roasting in inert gas to obtain the modified alumina carrier. And (3) after immersing the metal solution in an equal volume, drying to obtain the hydrotreating catalyst. The catalyst solves the problem of high ratio of L acid on the surface of the alumina carrier, and effectively weakens the strong interaction between the active metal and the carrier. The catalyst shows good hydrodenitrogenation and desulfurization activities.
Chinese patent CN 106669786a discloses a catalytic diesel hydrocracking catalyst and a preparation method thereof, wherein modified molecular sieve, amorphous silica-alumina and/or alumina are mixed first, and then molded to prepare a catalyst carrier. Impregnating or adsorbing unsaturated olefin on a carrier, reacting in an inert atmosphere for carbonization, and roasting to remove part of carbon deposit to obtain the carbon-containing carrier. Impregnating active metal, and drying to obtain the catalyst. The infrared acid strength distribution of the catalyst becomes reasonable, and the catalyst also shows better reaction activity and stability.
The preparation methods can change the surface acidity of the alumina carrier and the interaction with metal by a direct or indirect method, so that the aim of improving the performance of the catalyst can be fulfilled. However, none of the methods used has the effect of directionally changing the acid centers, and only the content of all the acid centers can be changed synchronously. When the raw materials with low aromatic hydrocarbon content are processed, the reasonable matching of the acid center and the hydrogenation center can be realized by improving the acid strength and the content, the catalyst activity is improved, and the more efficient desulfurization and denitrification processes are realized under the condition of lower reaction temperature.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a hydrogenation pretreatment catalyst and a preparation method and application thereof. The catalyst has richer medium and strong acid, can obviously improve the synergistic effect of active metal and an acid center, and improves the activity of the catalyst.
A hydrotreating catalyst takes carbon-containing alumina as a carrier, takes VIB group metal oxide and/or VIII group metal oxide as active components, and takes the weight of the final hydrotreating catalyst as the reference, the mass content of carbon is 0.10-1.90 wt%, preferably 0.12-1.70 wt%. In pyridine infrared acid in the hydrogenation pretreatment catalyst, the acid amount of more than 300 ℃ is 0.160 mmol/g-0.205 mmol/g, preferably 0.165 mmol/g-0.195 mmol/g.
In the catalyst, the total pyridine infrared acid amount of the hydrogenation pretreatment catalyst is 0.490-0.645 mmol/g, preferably 0.495-0.635 mmol/g.
In the catalyst, the ratio of the total pyridine infrared acid amount to the acid amount of which the temperature is higher than 300 ℃ is 3.00-3.50, preferably 3.08-3.45.
In the catalyst, the weight of the final hydrogenation pretreatment catalyst is taken as the reference, the weight of the VIB group metal oxide in the catalyst is 5% -30%, preferably 10% -28%, and the weight of the VIII group metal oxide in the catalyst is 1% -10%, preferably 2% -8%. The group VIB metal may be molybdenum and/or tungsten and the group VIII metal may be cobalt and/or nickel.
In the catalyst of the invention, the specific surface area of the catalyst is 155m 2/g~190m2/g, preferably 160m 2/g~185m2/g; the pore volume is 0.35mL/g to 0.43mL/g, preferably 0.37mL/g to 0.43mL/g.
In the catalyst of the present invention, the hydrotreating catalyst may be one of sphere, bar (such as clover, clover or cylindrical bar), ring, plate, bird nest.
A method of preparing a hydroprocessing catalyst, the method comprising:
firstly, introducing a VIB metal and/or a VIII metal component into a carbon-containing alumina carrier;
Then, drying and roasting to obtain the final hydrogenation pretreatment catalyst;
Wherein the carbon-containing alumina carrier is 1.00-4.10 wt% of carbon, preferably 1.20-3.90 wt% of carbon based on the weight of the carbon-containing alumina carrier; in pyridine infrared acid corresponding to the carbon-containing alumina carrier, the acid amount at the temperature of more than 300 ℃ is 0.125 mmol/g-0.205 mmol/g, preferably 0.135 mmol/g-0.200 mmol/g; the ratio of the total infrared acid amount of pyridine containing carbon aluminum oxide to the acid amount of the pyridine containing carbon aluminum oxide at the temperature of more than 300 ℃ is 3.25-4.45, and is preferably 3.33-4.40. In the carbon-containing alumina carrier, the total infrared acid content of pyridine is 0.575 mmol/g-0.665 mmol/g, preferably 0.590 mmol/g-0.650 mmol/g.
In the method of the invention, the specific surface area of the carbon-containing alumina is 225m 2/g~305m2/g, preferably 235m 2/g~295m2/g; the pore volume is 0.53mL/g to 0.70mL/g, preferably 0.56mL/g to 0.68mL/g.
In the method of the invention, the preparation method of the carbon-containing alumina comprises the following steps of firstly vacuumizing the alumina; and then carrying out carbon deposition on the treated alumina to obtain the final carbon-containing alumina.
In the preparation of the carbonaceous alumina of the invention, the alumina may be prepared by commercial products or according to the prior art; alumina powder may be used, or alumina after molding may be used, and alumina after molding is preferable. The shaped aluminum oxide can be one of sphere, strip (such as clover, clover or cylindrical strip), ring, sheet and bird nest. Optionally, the alumina contains an auxiliary agent, wherein the auxiliary agent component can be one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron and the like, and the content of the auxiliary agent is below 10wt%, preferably below 8wt%, based on the weight of the carbon-containing alumina.
In the preparation of the carbon-containing alumina, the conditions of the vacuumizing treatment are as follows: the pressure is controlled to be 0.01kPa to 0.80kPa, preferably 0.01kPa to 0.60kPa, the treatment temperature is 250 ℃ to 450 ℃, preferably 260 ℃ to 430 ℃, and the treatment time can be 2 hours to 8 hours, preferably 3 hours to 6 hours.
In the preparation of the carbon-containing alumina of the present invention, the carbon number of the carbon source compound reacting with the vacuum-treated alumina is selected to be 1 to 20, for example: monohydric aliphatic alcohols such as methanol and ethanol; olefins, diolefins, alkanes, branched aromatic hydrocarbons; pyridine and pyridine homologs; and the central atom contains one or a combination of more of alkylamine, mercaptan, trialkylphosphine and the like with lone pair electrons.
In the preparation of the carbon-containing alumina, the carbon deposition treatment condition is that the gas flow rate is 0.5 m/s-8.0 m/s, preferably 0.6 m/s-6.0 m/s; the airspeed is 0.1 to 2.0, preferably 0.5 to 1.8. The molar ratio of the carrier gas to the carbon-containing compound is controlled to be 80:1-500:1, preferably 100:1-400:1.
In the method of the invention, the carbon deposition treatment conditions are as follows: the pressure range can be controlled to be 0.1-2.0 MPa, preferably 0.1-1.8 MPa, the system temperature is 260-400 ℃, preferably 280-380 ℃, and the reaction time is 1-10 h, preferably 2-8 h.
In the method of the invention, the group VIB metal is preferably molybdenum and/or tungsten, the group VIII metal is preferably nickel and/or cobalt, the group VIB metal and the group VIII metal can be from salts, oxides or acid and other reagents, for example, molybdenum element can be one or more of molybdenum oxide, ammonium molybdate and ammonium paramolybdate, and tungsten element can be one or more of ammonium metatungstate, nickel is selected from nickel nitrate, nickel carbonate, basic nickel carbonate, nickel chloride and nickel oxalate. The process of preparing the metal solution is well known to those skilled in the art.
In the method, the active metal components of the VIB metal oxide and/or the VIII metal oxide are loaded on the carbon-containing alumina carrier by adopting an impregnation method, and the process can adopt equal volume impregnation and excessive impregnation; either stepwise or co-impregnation, preferably isovolumetric co-impregnation, may be used. After the impregnation, a proper curing process is required, wherein the curing temperature is 20-55 ℃, preferably 25-50 ℃, and the curing time is 2-24 hours, preferably 3-18 hours. The drying temperature is 90-180 ℃, preferably 110-150 ℃, and the drying time is 3-12 h, preferably 5-10 h.
In the method, the carbon-containing alumina loaded with metal is directly transferred into a roasting furnace with a set temperature, and is treated under the condition of air or oxygen-containing atmosphere, wherein the roasting temperature is 330-520 ℃, preferably 350-510 ℃, and the roasting time is 20-180 min, preferably 30-150 min.
The hydrogenation pretreatment catalyst is applied to a hydrocracking device, the processing raw oil can be any one or mixed oil of straight-run diesel oil and straight-run wax oil, the distillation range is 180-570 ℃, the dry point is 520-570 ℃, the nitrogen content is 200-2500 mug/g, and the sulfur content is not strictly limited.
The application of the hydrotreating catalyst, wherein the operating conditions are as follows: the reaction temperature is 310-410 ℃, preferably 330-400 ℃, and the reaction inlet pressure is 6-16 MPa, preferably 8-14 MPa; space velocity is 0.5h -1~3.0h-1, preferably 0.6h -1~2.5h-1; the volume ratio of hydrogen to oil at the reaction inlet is 400-1200, preferably 500-1100.
The method of the invention activates alumina by using high temperature and vacuum conditions, fully exposes acid sites on the surface of the carrier, carries out selective carbon deposition under specific conditions, covers strong acid centers in part and exposes other relatively weaker acid centers. The active metal component is then coated onto the exposed acid sites and the carbon deposit surface. And (3) controlling the roasting process, properly removing part of carbon deposit, exposing strong acid centers in the carbon-covered part, and forming coordinated active centers with surrounding metal centers. Meanwhile, the residual carbon deposit can weaken the interaction force between the active metal and the surface of the carrier, and the metal utilization rate is improved. Through the shielding effect of proper fixed-point carbon deposition, the acid loss in the metal loading process is avoided, so that the catalyst has more acid centers with concentrated acid strength and metal centers with higher hydrogenation/hydrogenolysis activity, and the catalyst activity can be improved by the mutual cooperation of the acid centers and the metal centers.
Detailed Description
The effect of the hydrotreating catalyst is further illustrated by the following examples and comparative examples, but the application should not be considered as being limited to the following examples, the percentages of materials in the context of the application, unless indicated otherwise, are by weight.
In the invention, the pore structure of the hydrotreatment catalyst after calcination is measured by a low-temperature nitrogen physical adsorption method. The acid content of the carrier with different intensities is determined by adopting a pyridine adsorption infrared spectrometry, and the specific process of pyridine adsorption is as follows: preparing a sample into a sheet, placing the sheet into an in-situ tank, activating the sheet for 3 hours at 350 ℃ in vacuum, and then performing infrared spectrum scanning to record as a spectrum 1; cooling to 150deg.C, adsorbing pyridine, vacuumizing at 150deg.C to remove alkaline molecules, and recording as map 2. And differentiating the map 2 and the map 1 to obtain a pyridine absorption peak at 150 ℃, integrating the peak splitting area by using a model-island FTIR-8400 Fourier transform infrared spectrometer with system software, and calculating the acid content in the sample at the temperature by adopting beer's law. And gradually heating to 300 ℃, and carrying out vacuumizing physical desorption to obtain a residual pyridine absorption peak in the test sample at a corresponding temperature, so that the corresponding acid content can be calculated.
The pore structure properties of the commercial clover shaped alumina supports containing 1.3% by weight of ZrO 2 used in the examples and comparative examples are: the pore volume is 0.71cm 3/g, and the specific surface area is 321m 2/g.
Example 1
This example is a method for preparing a carbon-containing support and a catalyst: the pressure of the container where the alumina-based carrier is located is regulated to be 0.05kPa, the temperature in the container is gradually increased to 255 ℃, and the temperature is kept constant for 5.5 hours. The temperature of the system was adjusted to 395℃and nitrogen was gradually introduced into the system to adjust the pressure of the system to 1.9MPa. Methanol was introduced into the reactor at a space velocity of 1.9, a feed molar ratio of nitrogen to methanol of 380:1, and a gas flow rate of 7.0m/s. And (3) introducing a carbon source for 1.8 hours, and then introducing nitrogen only for constant-temperature purging to obtain the carbon-containing alumina carrier CT-1.
Calculated according to the weight of the catalyst: the nickel oxide was prepared as a metal solution of 4.2wt% and the molybdenum oxide was prepared as a metal solution of 22.3wt%, and the molybdenum nickel solution was impregnated on the carbonaceous support by the isovolumetric impregnation method. Then preserving for 20 hours at 30 ℃, and keeping for 4 hours in a drying oven at 170 ℃. Transferring to an air atmosphere, and roasting in a roasting furnace at 513 ℃ for 20min to obtain the catalyst CC-1.
Example 2
This example is a method for preparing a carbon-containing support and a catalyst: the pressure of the container in which the alumina-based carrier is positioned is regulated to be 0.70kPa, the temperature in the container is gradually increased to 440 ℃, and the temperature is kept constant for 2.5 hours. The temperature of the system is adjusted to 360 ℃, nitrogen is gradually introduced into the system, and the pressure of the system is adjusted to 1.5Mpa. Methanol was introduced into the reactor at a space velocity of 1.5, a molar ratio of nitrogen to methanol of 180:1, and a gas flow rate of 1.6m/s. And after 3.2 hours, only introducing nitrogen to perform constant-temperature purging to obtain the carbon-containing alumina carrier CT-2.
Calculated according to the weight of the catalyst: a metal solution of 4.2wt% nickel oxide and 22.3wt% molybdenum oxide was prepared and impregnated onto a carbon-containing support with an equal volume. Then, the mixture was left to stand at 45℃for 15 hours and kept in a drying oven at 100℃for 11 hours.
Transferring the mixture into a roasting furnace with air atmosphere and 480 ℃ for 100min to obtain a catalyst CC-2;
transferring to a roasting furnace with air atmosphere and temperature of 430 ℃ for roasting for 120min to obtain a catalyst CC-3;
transferring to a roasting furnace with air atmosphere and 380 ℃ for roasting for 120min to obtain a catalyst CC-4;
Example 3
The pressure of the container where the alumina-based carrier is positioned is regulated to be 0.24KPa, the temperature in the container is gradually increased to 315 ℃, and the temperature is kept constant for 4.5 hours. The temperature of the system was adjusted to 270℃and nitrogen was gradually introduced into the system to adjust the pressure of the system to 0.3MPa. Butadiene was introduced into the reactor at a space velocity of 0.6, a molar ratio of nitrogen to methanol of 200:1, and a gas flow rate of 2.5m/s. And after the carbon source is introduced for 9.0h, only nitrogen is introduced for constant-temperature purging, so as to obtain the carbon-containing alumina carrier CT-3.
Calculated according to the weight of the catalyst: a metal solution of 4.2wt% nickel oxide and 22.3wt% molybdenum oxide was prepared and the molybdenum nickel solution was impregnated onto a carbon-containing support with an equal volume. Then preserving for 4 hours at 50 ℃, and keeping the temperature in a drying oven at 145 ℃ for 8 hours. Transferring to a roasting furnace with air atmosphere at 336 ℃ for roasting for 90min to obtain the catalyst CC-5.
Example 4
The pressure of the container where the alumina-based carrier is positioned is regulated to be 0.45KPa, the temperature in the container is gradually increased to 430 ℃, and the temperature is kept constant for 5.5 hours. The temperature of the system is adjusted to 400 ℃, nitrogen is gradually introduced into the system, and the pressure of the system is adjusted to 1.8Mpa. Tert-butylbenzene was introduced into the reactor at a space velocity controlled to 0.3, a molar ratio of nitrogen to tert-butylbenzene of 400:1, and a gas flow rate of 1.8m/s. And after introducing a carbon source for 9 hours, only introducing nitrogen to perform constant-temperature purging, so as to obtain the carbon-containing alumina carrier CT-4.
Calculated according to the weight of the catalyst: a metal solution of 4.2wt% nickel oxide and 22.3wt% molybdenum oxide was prepared and the molybdenum nickel solution was impregnated onto the carbonaceous support by an isovolumetric impregnation method. Then preserving for 6 hours at 35 ℃, and keeping for 6 hours in a drying oven at 120 ℃. Transferring to a roasting furnace with air atmosphere at 350 ℃ for 50min to obtain the catalyst CC-6.
Comparative example 1
Calculated according to the weight of the catalyst: a metal solution of 4.2wt% nickel oxide and 22.3wt% molybdenum oxide was prepared. The molybdenum nickel solution was impregnated into untreated commercial clover alumina DCT-1 using an equal volume impregnation method. The impregnated and loaded sample was incubated at 35℃for 8h, followed by 6h in a 120℃oven. Transferring to a roasting furnace with air atmosphere temperature of 480 ℃ for roasting for 45min, and obtaining the catalyst DC-1.
Example 5
This example is an activity evaluation experiment of the catalyst:
All prepared catalysts were evaluated on a 100mL small hydrogenation unit, and the hydrodesulfurization and hydrodenitrogenation activities of the catalysts were evaluated using straight run wax oil as the feed oil. Evaluation of the operating conditions of the experiment: the reaction temperature is 340 ℃, the reaction pressure is 14.0Mpa, the space velocity is 1.6h -1, and the hydrogen-oil volume ratio is 600:1.
TABLE 1 basic Properties of raw oil
Table 2 examples and comparative examples carrier properties
Table 3 catalyst properties and catalytic activity for examples and comparative examples
* The relative activity was based on the catalytic activity of comparative example DC-1.
In conclusion, the physicochemical properties and catalytic activity of the obtained catalyst can be seen that the indiscriminate coverage of the active metal in the acid center can be avoided by dipping the metal on the carbon-containing alumina and then carrying out controlled roasting treatment, so that more medium and strong acid centers are exposed, the acid strength distribution of the catalyst is optimized, and the hydrodesulfurization and hydrodenitrogenation performances of the catalyst are comprehensively improved.
Claims (26)
1. A hydrotreating catalyst, characterized in that: the catalyst takes carbon-containing alumina as a carrier, takes VIB metal oxide and/or VIII metal oxide as active components, takes the weight of the final hydrotreating catalyst as a reference, and has the mass content of carbon of 0.10-1.90 wt%, pyridine infrared acid of the hydrotreating catalyst, and the acid quantity of more than 300 ℃ is 0.160-0.205 mmol/g; the preparation method of the carbon-containing alumina comprises the following steps of firstly vacuumizing the alumina; then carrying out carbon deposition on the treated alumina to obtain final carbon-containing alumina; the conditions of the vacuumizing treatment are as follows: the pressure is controlled to be 0.01kPa to 0.80kPa, the treatment temperature is 250 ℃ to 450 ℃ and the treatment time is 2 hours to 8 hours; the carbon deposition treatment conditions are as follows: the gas flow rate is 0.5 m/s-8.0 m/s; airspeed is 0.1-2.0; the molar ratio of the carrier gas to the carbon-containing compound is controlled to be 80:1-500:1; the pressure range is controlled to be 0.1-2.0 MPa, the system temperature is 260-400 ℃, and the reaction time is 1-10 h.
2. The catalyst of claim 1, wherein: based on the weight of the final hydrotreating catalyst, the mass content of carbon is 0.12-1.70 wt%, and the acid content of the hydrotreating catalyst pyridine infrared acid is 0.165-0.195 mmol/g at the temperature of more than 300 ℃.
3. The catalyst of claim 1, wherein: the total pyridine infrared acid amount of the hydrogenation pretreatment catalyst is 0.490-0.645 mmol/g.
4. A catalyst according to claim 3, characterized in that: the total pyridine infrared acid amount of the hydrogenation pretreatment catalyst is 0.495 mmol/g-0.635 mmol/g.
5. The catalyst of claim 1, wherein: the ratio of the total pyridine infrared acid amount to the acid amount of which the temperature is higher than 300 ℃ of the hydrogenation pretreatment catalyst is 3.00-3.50.
6. The catalyst of claim 5, wherein: the ratio of the total pyridine infrared acid amount to the acid amount of which the temperature is higher than 300 ℃ of the hydrogenation pretreatment catalyst is 3.08-3.45.
7. The catalyst of claim 1, wherein: based on the weight of the final hydrogenation pretreatment catalyst, the content of the VIB group metal oxide in the catalyst is 5% -30%, and the content of the VIII group metal oxide in the catalyst is 1% -10%.
8. The catalyst of claim 7, wherein: based on the weight of the final hydrogenation pretreatment catalyst, the content of the VIB group metal oxide in the catalyst is 10% -28%, and the content of the VIII group metal oxide in the catalyst is 2% -8%.
9. The catalyst according to claim 7 or 8, characterized in that: the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel.
10. The catalyst of claim 1, wherein: the specific surface area of the catalyst is 155m 2/g~190m2/g; the pore volume is 0.35 mL/g-0.43 mL/g.
11. The catalyst of claim 10, wherein: the specific surface area of the catalyst is 160m 2/g~185m2/g; the pore volume is 0.37 mL/g-0.43 mL/g.
12. The catalyst of claim 1, wherein: the hydrogenation pretreatment catalyst is one of sphere, strip, ring, sheet and bird nest.
13. A process for the preparation of a hydroprocessed catalyst according to any one of claims 1 to 12, characterized in that: the method comprises the following steps:
firstly, introducing a VIB metal and/or a VIII metal component into a carbon-containing alumina carrier;
and then drying and roasting to obtain the final hydrogenation pretreatment catalyst.
14. The method according to claim 13, wherein: the carbon-containing alumina carrier is based on the weight of the carbon-containing alumina carrier, and the carbon content is 1.00-4.10 wt%; in pyridine infrared acid corresponding to the carbon-containing alumina carrier, the acid amount at the temperature of more than 300 ℃ is 0.125 mmol/g-0.205 mmol/g.
15. The method according to claim 14, wherein: the carbon-containing alumina carrier is based on the weight of the carbon-containing alumina carrier, and the carbon content is 1.20-3.90 wt%; in pyridine infrared acid corresponding to the carbon-containing alumina carrier, the acid amount at the temperature of more than 300 ℃ is 0.135 mmol/g-0.200 mmol/g.
16. The method according to claim 14 or 15, characterized in that: the ratio of the total pyridine infrared acid amount to the acid amount which is more than 300 ℃ of the carbon-containing alumina carrier is 3.25-4.45; in the carbon-containing alumina carrier, the total infrared acid content of pyridine is 0.575 mmol/g-0.665 mmol/g.
17. The method according to claim 16, wherein: the ratio of the total pyridine infrared acid amount to the acid amount which is more than 300 ℃ of the carbon-containing alumina carrier is 3.33-4.40; in the carbon-containing alumina carrier, the total infrared acid content of pyridine is 0.590 mmol/g-0.650 mmol/g.
18. The method according to claim 14 or 15, characterized in that: the specific surface area of the carbon-containing alumina carrier is 225m 2/g~305m2/g; the pore volume is 0.53 mL/g-0.70 mL/g.
19. The method according to claim 18, wherein: the specific surface area of the carbon-containing alumina carrier is 235m 2/g~295m2/g; the pore volume is 0.56 mL/g-0.68 mL/g.
20. The method according to claim 13, wherein: the group VIB metal is molybdenum and/or tungsten, and the group VIII metal is nickel and/or cobalt.
21. The method according to claim 13, wherein: the VIB metal and the VIII metal are one or more of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, nickel nitrate, nickel carbonate, basic nickel carbonate, nickel chloride and nickel oxalate.
22. The method according to claim 13, wherein: the active metal components of the VIB metal oxide and/or the VIII metal oxide are supported on the carbon-containing alumina carrier in a sharing way by adopting an impregnation method.
23. The method according to claim 13, wherein: the drying temperature is 90-180 ℃ and the drying time is 3-12 h; the roasting temperature is 330-520 ℃ and the roasting time is 20-180 min.
24. The method according to claim 23, wherein: the drying temperature is 110-150 ℃ and the drying time is 5-10 hours; the roasting temperature is 350-510 ℃, and the roasting time is 30-150 min.
25. Use of a hydroprocessed catalyst according to any one of claims 1 to 12, characterized in that: the operating conditions were as follows: the reaction temperature is 310-410 ℃, and the reaction inlet pressure is 6-16 MPa; airspeed is 0.5h -1~3.0h-1; the volume ratio of hydrogen to oil at the reaction inlet is 400-1200.
26. The use according to claim 25, characterized in that: the operating conditions were as follows: the reaction temperature is 330-400 ℃, and the reaction inlet pressure is 8-14 MPa; airspeed is 0.6h -1~2.5h-1; the volume ratio of hydrogen to oil at the reaction inlet is 500-1100.
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