CN116984010A - Residual oil hydrogenation catalyst, preparation method and application thereof - Google Patents
Residual oil hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- CN116984010A CN116984010A CN202210447894.3A CN202210447894A CN116984010A CN 116984010 A CN116984010 A CN 116984010A CN 202210447894 A CN202210447894 A CN 202210447894A CN 116984010 A CN116984010 A CN 116984010A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 238000001035 drying Methods 0.000 claims abstract description 27
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 24
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 239000012876 carrier material Substances 0.000 claims abstract description 6
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- -1 VIB metal oxide Chemical class 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 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 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 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
- B01J27/24—Nitrogen compounds
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a residual oil hydrogenation catalyst, a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: impregnating a first active metal solution into porous carbon nitrogen/SiO 2 Drying and roasting the composite carrier to obtain a metal/composite carrier material; preparing a pseudo-boehmite wet filter cake, and drying to prepare the pseudo-boehmite; mixing the metal/composite carrier with pseudo-boehmite, forming, and drying to obtain a catalyst precursor; then impregnating with second active metal solution, drying and roasting to obtain the catalyst. The catalyst provided by the invention is suitable for residual oil hydrogenation treatment, and particularly has excellent catalytic performance in desulfurization and denitrification.
Description
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method and application thereof, in particular to a residual oil hydrogenation catalyst and a preparation method and application thereof.
Background
The residual oil hydrogenation catalyst is mainly a metal supported catalyst, and alumina and/or silica are/is mainly used as a carrier, and Ni, mo, co and the like are used as active metal components. In the existing method, when the active metal load is large, the phenomenon of agglomeration or uneven distribution of metal particles is easy to occur. In addition, in the roasting process, the formation of metal-oxygen-aluminum bonds can be caused due to the strong interaction between the metal and the carrier, so that the catalytic efficiency of the catalyst is affected, and finally, the hydrogenation activity of the catalyst is reduced. The alumina carrier has proper amount of silica to raise the acidity and specific surface area of alumina, and to facilitate polymerization and hydrogenation reaction.
CN103055908A discloses a method for preparing a hydrotreating catalyst. Firstly pulping aluminum hydroxide or aluminum oxide to prepare slurry, and adding concentrated phosphoric acid to react to obtain sol; then taking the sol as a binder, kneading with macroporous alumina and small pore alumina, forming, drying and roasting to obtain an alumina carrier; then, the alumina carrier is impregnated with the active metal component impregnation liquid, and the hydrotreating catalyst is prepared by drying and roasting. The method is complex to operate, the introduction of acid sites can promote the bonding between active metal and a carrier, a large amount of concentrated acid can cause environmental pollution, and industrial production is dangerous.
CN105582945a discloses a method for preparing a hydrotreating catalyst. The method comprises the steps of firstly soaking an alumina carrier by using urea aqueous solution, then spraying and soaking the alumina carrier by using polyol or monosaccharide aqueous solution according to the sequence from high to low in concentration, so that the concentration of the polyol and/or monosaccharide is distributed on the carrier in a gradient manner from outside to inside, and then loading active metal components.
CN1257754a discloses a preparation method of a silica-alumina catalyst carrier, a silica-alumina precursor is prepared by introducing sodium silicate and aluminum sulfate, the pore volume of the prepared carrier is 0.45-0.75 mL/g, and the average pore diameter is 5-10nm. However, the final synthetic silica-alumina carrier has a smaller pore diameter and is not suitable for use as a hydrotreating catalyst for heavy oils or residues having a larger molecular weight.
CN1169614C discloses a preparation method of silicon-containing aluminum hydroxide, by introducing a certain amount of sodium silicate during the gelling process of preparing aluminum hydroxide by carbonization and continuing to add a certain amount of sodium silicate during the subsequent aging process, silicon-containing aluminum oxide can be prepared, which has a smaller average pore diameter, and although suitable for heavy oil or residual oil hydrodesulfurization or hydrodenitrogenation catalysts, the pore diameter is smaller for residual oil hydrodemetallization catalysts, which needs further improvement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a residual oil hydrogenation catalyst, and a preparation method and application thereof. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, proper surface acidity and suitability for residual oil hydrogenation treatment.
The invention provides a preparation method of a residual oil hydrogenation catalyst, which comprises the following steps:
(1) Impregnating a first active metal solution into porous carbon nitrogen/SiO 2 Drying and roasting the composite carrier to obtain a metal/composite carrier material;
(2) Preparing a pseudo-boehmite wet filter cake, and drying to prepare the pseudo-boehmite;
(3) Mixing the metal/composite carrier obtained in the step (1) with the pseudo-boehmite obtained in the step (2), forming, and drying to obtain a catalyst precursor;
(4) And (3) impregnating the catalyst precursor prepared in the step (3) with a second active metal solution, drying and roasting to prepare the catalyst.
In the present invention, in the step (1), the porous carbon nitrogen/SiO 2 A composite carrier comprising:
(a) Dissolving cyanamide in silica sol, stirring, and adding an organic solvent to form gel;
(b) The gel is heated and roasted in inert atmosphere to obtain porous carbon nitrogen/SiO 2 And (3) a composite carrier, and grinding the composite carrier into powder.
In the method of the present invention, in step (a), the silica sol concentration is SiO 2 30 to 55 percent, preferably 40 to 50 percent.
In the method of the present invention, in the step (a), the mass ratio of the addition amount of the cyanamide to the silica sol is 0.5 to 1.5, preferably 0.6 to 1.2.
In the method of the present invention, in the step (a), the organic solvent is selected from one of ethanol and ethylene glycol, preferably ethanol, and the mass ratio of the added amount to the silica sol is 0.5-1.5.
In the process of the present invention, in step (b), the firing temperature is 250 to 650 ℃, preferably 300 to 450 ℃, for 2 to 15 hours, and the inert atmosphere is selected from Ar, he, N 2 At least one of them.
In the method of the present invention, in the step (1), the active metal in the first active metal solution is at least one selected from cobalt and nickel, preferably nickel, which are metals of group VIII; the load is 30% -50% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide; wherein the concentration of the first active metal solution calculated by active metal oxide is 0.02-0.40 g/mL.
In the method, in the step (1), the drying temperature is 100-120 ℃ and the drying time is 2-5 h; the roasting temperature is 400-450 ℃, the inert atmosphere is introduced for protection for 2-3 hours, and the inert atmosphere is selected from Ar, he and N 2 At least one of them.
In the method of the invention, in the step (2), the method for preparing the pseudo-boehmite wet filter cake comprises the following steps:
(A) Adding a first alkaline solution into a first reaction kettle, and introducing a mixed gas containing carbon dioxide to react so that the pH value of the system is 2-4;
(B) Adding bottom water into a second reaction kettle, heating to a reaction temperature, and then adding a second alkaline solution and the material obtained in the step (A) into the second reaction kettle in parallel flow for reaction;
(C) And (3) aging the slurry obtained after the reaction in the step (B), filtering and washing after the aging is finished to obtain the pseudo-boehmite filter cake.
In the method of the present invention, in the step (a), the first alkaline solution is one or two of a sodium metaaluminate solution or a potassium metaaluminate solution, preferably a sodium metaaluminate solution; the saidThe concentration of the sodium metaaluminate solution and/or the potassium metaaluminate is Al 2 O 3 10-30 g Al 2 O 3 and/L, wherein the caustic ratio of the first alkaline solution is 1.35-1.65.
In the method, in the step (A), the volume of the first alkaline solution added into the first reaction kettle is 2/3-3/4 of the volume of the first reaction kettle; the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% -70%; the carbon dioxide-containing mixed gas may be a mixed gas of carbon dioxide and air.
In the method of the invention, in the step (A), the initial reaction temperature of the reaction carried out by introducing the mixed gas containing carbon dioxide is 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process does not need to be cooled to keep low temperature, and the temperature of the slurry is 40-75 ℃ at the end of the reaction.
In the method of the present invention, in the step (B), the second alkaline solution is one or two of a sodium metaaluminate solution or a potassium metaaluminate solution, preferably a sodium metaaluminate solution; the concentration of sodium metaaluminate and/or potassium metaaluminate in the second alkaline solution is Al 2 O 3 130-350 g Al 2 O 3 Preferably 150 to 250g Al 2 O 3 and/L, the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.10-1.40, preferably 1.15-1.35.
In the method of the invention, in the step (B), the bottom water added into the second reaction kettle is 1/10-1/5 of the volume of the second reaction kettle.
In the method, in the step (B), the materials obtained in the step (A) are added into a second reaction kettle, and the material adding time is controlled to be 60-150 min. Further, in the step (B), the second alkaline solution and the material obtained in the step (A) are added into a second reaction kettle in parallel flow for reaction, and the pH value is controlled to be 7.5-9.0.
In the process of the present invention, in step (B), the reaction is carried out with stirring. The reaction temperature of the reaction is 40 to 70 ℃, preferably 45 to 65 ℃.
In the method of the present invention, in the step (C), the aging conditions are: the temperature is 50-95 ℃ and the time is 30-20 min.
In the process of the present invention, in step (C), the washing may be carried out by a washing method conventional in the art, preferably by deionized water at 50℃to 80℃to neutrality.
In the method of the invention, in the step (C), the solid content of the obtained pseudo-boehmite wet filter cake is 30-45 wt%.
In the method of the invention, in the step (2), the drying temperature is 60-150 ℃ and the drying time is 4-10 h.
In the method, in the step (3), the mass ratio of the metal/composite carrier material obtained in the step (1) to the pseudo-boehmite is 0.05-0.3. The molding can be extrusion molding. Extrusion aids can be added in the forming process, and the extrusion aids can be sesbania powder, and the addition amount of the extrusion aids is 1-6% of the mass of the pseudo-boehmite.
In the method, in the step (3), the drying temperature is 80-120 ℃ and the time is 4-6 h.
In the method of the present invention, in the step (4), the impregnation is saturated impregnation. The active metal in the second active metal solution is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Ni; wherein the concentration of the VIB group metal in the second active metal solution is 0.05-0.5 g/mL in terms of oxide, and the concentration of the VIII group metal in terms of oxide is 0.01-0.2 g/mL.
In the method of the invention, the amount of the VIII group metal introduced into the catalyst from the step (4) accounts for 50-70% of the mass of the VIII group total metal oxide in the catalyst in terms of oxide.
In the method of the invention, in the step (4), the content of the oxide of the VIB group metal is 10-30% and the content of the oxide of the VIII group metal is 2-15% based on the mass of the catalyst.
In the method, in the step (4), the drying temperature is 80-120 ℃, the drying time is 2-5 hours, the drying is carried out, the roasting temperature is 600-900 ℃, and the roasting time is controlled to be 3-5 hours.
In a second aspect the present invention provides a residuum hydrogenation catalyst obtainable by the process of the first aspect.
In the catalyst, the active metal is at least one of group VIB metals and at least one of group VIII metals, wherein the group VIB metals are preferably at least one of Mo and W, more preferably Mo, and the group VIII metals are preferably at least one of Co and Ni, more preferably Ni.
In the catalyst, the content of the metal oxide of the VIB group is 10-30% and the content of the metal oxide of the VIII group is 2-15% based on the mass of the catalyst.
In the invention, the content of silicon oxide in the catalyst is 8-20% based on the mass of the catalyst.
In the invention, the catalyst also contains N, and the content of N calculated by simple substance is 0.5-1.0% based on the mass of the catalyst.
In the catalyst, the dispersity of the active metal is as follows: i VIB /I Al (. Times.100) is 3-10, I VIII /I Al (. Times.100) is 3 to 9.
In the invention, the specific surface area of the catalyst is 140-230 m 2 Preferably 170 to 200m 2 Per gram, the pore volume is 0.5-1.2 cm 3 Preferably 0.7 to 0.9cm per gram 3 And/g, the mechanical strength is 16-27N/mm, preferably 18-24N/mm, the pore volume of the pores with the pore diameter of 15-80 nm accounts for 6-23% of the total pore volume, preferably 10-14%, and the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 8%, preferably 4-7% of the total pore volume.
In the present invention, the acid amount of the catalyst is 0.4 to 0.9mmol/g, preferably 0.6 to 0.8mmol/g. Ratio C of the amount of acid B to the amount of acid L B /C L 0.02 to 0.09, preferably 0.04 to 0.07.
The third aspect of the invention provides the application of the residuum hydrogenation catalyst in residuum hydrogenation technology.
In the invention, the residuum and hydrogen-containing gas are contacted and reacted under the hydrogenation reaction condition in the presence of the residuum hydrogenation catalyst or the residuum hydrogenation catalyst obtained according to the preparation method.
In the residual oil hydrogenation reaction, the residual oil material is selected from one of atmospheric residual oil, vacuum residual oil and high-temperature coal tar.
In the above-mentioned residuum hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixed gas of hydrogen and other gases, and the hydrogen volume content in the mixed gas is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.
In the residuum hydrogenation process, the residuum hydrogenation operation conditions are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, and the liquid hourly space velocity is 0.1-3.0 h -1 The volume ratio of the hydrogen oil is 100-1000.
Compared with the prior art, the invention has the following beneficial effects:
the residual oil hydrogenation catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, proper surface acidity, excellent catalytic performance in desulfurization and denitrification, and good activity in the aspects of carbon residue removal and demetallization, and is applied to residual oil hydrogenation treatment.
In the preparation method of the residual oil hydrogenation catalyst, on one hand, the cyanamide is subjected to thermal polymerization reaction in the silica sol to form the nitrogen-carbon composite carrier containing silicon dioxide, and as the nitrogen-carbon carrier has a certain band gap, and the size of the band gap can be adjusted by adjusting the roasting temperature, a metal-semiconductor heterojunction can be formed in the loading process of the nitrogen-carbon carrier and VIII group metal, so that the interaction force between the metal and the nitrogen-carbon carrier is enhanced, the metal dispersibility is improved, the metal loading capacity is increased, the electron migration efficiency between the active metal and aluminum oxide is greatly weakened, the adsorption and bonding effect between the active metal and aluminum oxide are weakened, and the activity of the synthesized catalyst is higher in the residual oil hydrogenation process. On the other hand, the nitrogen-carbon carrier contains a large amount of silicon dioxide balls, the nitrogen-carbon carrier is baked in an air atmosphere after secondary impregnation, the carbon carrier can be removed, the silicon dioxide balls enter the alumina carrier, silicon element not only plays a role of reaming, but also can adjust the surface acidity of the alumina carrier to form the silicon-containing hydrogenation catalyst, and the synthesis method is efficient and adjustable, and can provide higher activity for the hydrogenation catalyst. In addition, the pseudo-boehmite wet filter cake gibbsite prepared by the method is low in gibbsite, high in crystallinity, and the alumina obtained by roasting has larger pore volume and pore diameter; meanwhile, the pseudo-boehmite wet filter cake prepared by the method has high peptization index, and provides a guarantee for preparing the high-side pressure strength carrier.
Detailed Description
In the invention, a nitrogen adsorption and desorption curve of a sample is tested by adopting an ASAP2020 type full-automatic physical adsorption instrument of Micromeritics company in the United states at the temperature of minus 196 ℃, and the specific surface area, pore volume and pore diameter distribution are measured.
In the invention, the mechanical strength is tested by using a ZQJ-III intelligent particle strength tester manufactured by Dalian Chi taking tester, and the average mechanical strength of a group of samples with the length of 4-6mm is measured.
In the invention, the metal dispersity is measured by XRS (the instrument is model Kratos Axis Ultra DLD) to measure XPS peak intensity ratio of active metal and aluminum element.
In the invention, the infrared acid amount is measured by using a Nicolet 870 type Fourier transform infrared spectrometer of Nicolet company in the United states.
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) A first 5000mL reactor was charged with Al having a caustic ratio of 1.45 and a concentration of 25g 2 O 3 The mixed solution of sodium metaaluminate of/L, then let in the mixed gas comprising carbon dioxide and air of 55% of the volume fraction of carbon dioxide, make system pH value drop to 3.4, the temperature of the supplies is 55 deg.C at the end of the reaction;
adding 1500mL of bottom water into 10000mL of second reaction kettle, starting a stirring and heating device, and heating to 65 ℃ at a flow rate of 35mL/minAdding the materials into a second reaction kettle for 90min, and adding 180gAl in parallel flow mode 2 O 3 And (3) controlling the pH value of the slurry in the second reaction kettle to be 8.0 by adjusting the flow rate of the sodium metaaluminate solution, keeping the temperature of the slurry in the second reaction kettle constant, finishing the reaction after the materials are used up, aging the slurry at 90 ℃ for 80min, washing the slurry to be neutral by deionized water at 70 ℃ after the aging is finished, filtering to obtain a pseudo-boehmite wet filter cake with 37% of solid content, and drying the pseudo-boehmite wet filter cake at 120 ℃ for 6 hours to obtain the required pseudo-boehmite.
(2) 10g of cyanamide was dissolved in 12.5g of silica sol having a concentration of 40%, and 12mL of absolute ethanol was then added with vigorous stirring to gel the solution. Transferring the gel into a crucible, heating to 400 ℃ in a tube furnace, keeping the temperature for 6 hours, introducing nitrogen for protection, and grinding the obtained sample into powder, namely porous carbon nitrogen/SiO 2 And (3) a composite carrier.
(3) 80mL of active metal solution with NiO content of 0.135g/mL is immersed into 100g of porous carbon nitrogen/SiO 2 Drying the composite carrier for 4 hours at 110 ℃, and roasting the composite carrier material for 3 hours at 430 ℃ under the protection of nitrogen atmosphere to obtain the metal/composite carrier material, wherein the mass of Ni introduced into the catalyst in the step (3) accounts for 31.3% of the total Ni in the catalyst.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain an intermediate.
(5) Preparing MoO-containing 3 The catalyst intermediate was saturated impregnated with an impregnating solution of 0.309g/mL and 0.058g/mL of NiO, dried at 120℃for 5 hours after the impregnation was completed, and calcined at 650℃for 3 hours to give the final hydrogenation catalyst A, the physicochemical properties of which are shown in Table 1.
Example 2
Other synthesis procedures were the same as in example 1 except that the addition amount of 40% silica sol was changed to 14.3g, to obtain a final hydrogenation catalyst B, the physicochemical properties of which are shown in Table 1.
Example 3
Other synthetic procedures as in the examples1, the difference is that the concentration of NiO in the impregnating solution in the first step is changed to 0.206g/mL, and the concentration of MoO in the impregnating solution in the second step is changed to 0.206g/mL 3 And NiO solution, wherein MoO 3 The concentration is changed to 0.312g/mL, the concentration of NiO is changed to 0.045g/mL, the roasting temperature is changed to 450 ℃ after impregnation, and the final hydrogenation catalyst C (the physical and chemical properties are shown in table 1) is obtained, wherein the mass of Ni introduced into the catalyst in the step (3) accounts for 46.9% of the total Ni in the catalyst.
Example 4
The other synthesis procedures were the same as in example 1 except that the addition amount of the metal/composite support material in step (4) was changed to 50g to obtain a final hydrogenation catalyst D, the physicochemical properties of which are shown in Table 1.
Comparative example 1
The other synthesis procedure was as in example 1, except that the carrier used was replaced by an equivalent amount of activated carbon powder. The final hydrogenation catalyst E was obtained, the physicochemical properties of which are shown in Table 1.
Comparative example 2
Other synthetic procedures were identical to example 1, except that:
(3) 80mL of active metal solution with NiO content of 0.284g/mL is immersed into 100g of porous carbon nitrogen/SiO 2 On the composite carrier, the Ni content of the catalyst introduced in the step (3) accounts for 64.5% of the total Ni content of the catalyst based on the mass of the oxide.
(5) Preparing MoO-containing 3 The impregnating solution, which was 0.312g/mL and 0.030g/mL of NiO, saturated impregnated the catalyst intermediate to give the final hydrogenation catalyst F, the physicochemical properties of which are shown in Table 1.
Comparative example 3
Other synthesis processes are the same as those of example 1, except that the pseudo-boehmite in step (1) is prepared by: 3000mL of 65gAl was added to a 5.0L reactor 2 O 3 And (3) introducing mixed gas of carbon dioxide with the carbon dioxide content of 80% (volume fraction) and air into the sodium metaaluminate solution with the caustic ratio of 1.35, wherein the initial reaction temperature is 25 ℃, cooling the solution to maintain the slurry temperature unchanged, and controlling the reaction time to be 45min to reduce the pH value of the sodium metaaluminate solution to 8.8. Filtering the slurry, washing with deionized water at 75deg.C, and drying at 120deg.C for 6 hrObtaining pseudo-boehmite. The final hydrogenation catalyst G was obtained, and its physicochemical properties are shown in Table 1.
Example 5
The catalysts obtained in examples 1 to 4 and comparative examples 1 to 3 were used in residuum hydrogenation reactions, respectively, the raw material properties are shown in Table 2, and the evaluation conditions and the evaluation results are shown in Table 3.
TABLE 1 physicochemical Properties of hydrogenation catalysts
TABLE 2 oil Properties of raw materials
| Density (20 ℃ C.) kg/m 3 | 986.3 |
| S，wt％ | 4.25 |
| N，ppm | 2439 |
| CCR，wt％ | 12.8 |
| Ni，ppm | 22.3 |
| V，ppm | 70.9 |
Table 3 evaluation conditions and evaluation results of the hydrogenation catalysts obtained in each example
Claims (17)
1. The preparation method of the residuum hydrogenation catalyst comprises the following steps:
(1) Impregnating a first active metal solution into porous carbon nitrogen/SiO 2 Drying and roasting the composite carrier to obtain a metal/composite carrier material;
(2) Preparing a pseudo-boehmite wet filter cake, and drying to prepare the pseudo-boehmite;
(3) Mixing the metal/composite carrier obtained in the step (1) with the pseudo-boehmite obtained in the step (2), forming, and drying to obtain a catalyst precursor;
(4) And (3) impregnating the catalyst precursor prepared in the step (3) with a second active metal solution, drying and roasting to prepare the catalyst.
2. The method of claim 1, wherein in step (1), the porous carbon nitrogen/SiO 2 A composite carrier comprising:
(a) Dissolving cyanamide in silica sol, stirring, and adding an organic solvent to form gel;
(b) The gel is heated and roasted in inert atmosphere to obtain porous carbon nitrogen/SiO 2 And (3) a composite carrier, and grinding the composite carrier into powder.
3. The method according to claim 1, wherein in the step (2), the method for producing a pseudo-boehmite wet cake comprises:
(A) Adding a first alkaline solution into a first reaction kettle, and introducing a mixed gas containing carbon dioxide to react so that the pH value of the system is 2-4;
(B) Adding bottom water into a second reaction kettle, heating to a reaction temperature, and then adding a second alkaline solution and the material obtained in the step (A) into the second reaction kettle in parallel flow for reaction;
(C) And (3) aging the slurry obtained after the reaction in the step (B), filtering and washing after the aging is finished to obtain the pseudo-boehmite filter cake.
4. The method according to claim 1, wherein in step (1), the active metal in the first active metal solution is selected from at least one of group VIII metal cobalt, nickel, preferably nickel; the concentration of the first active metal solution calculated by active metal oxide is 0.02-0.40 g/mL.
5. The method according to claim 1, wherein in the step (1), the drying temperature is 100 to 120 ℃ for 2 to 5 hours; the roasting temperature is 400-450 ℃, the inert atmosphere is introduced for protection for 2-3 hours, and the inert atmosphere is selected from Ar, he and N 2 At least one of them.
6. The method according to claim 1, wherein in the step (3), the mass ratio of the metal/composite support material to pseudo-boehmite is 0.05 to 0.3.
7. The method of claim 1, wherein in step (4), the impregnation is saturated impregnation; the active metal in the second active metal solution is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Ni; wherein the concentration of the VIB group metal in the second active metal solution is 0.05-0.5 g/mL in terms of oxide, and the concentration of the VIII group metal in terms of oxide is 0.01-0.2 g/mL.
8. The preparation method according to claim 1, wherein the amount of the group VIII metal introduced into the catalyst from step (1) is 30% to 50% by mass of the total active metal oxide of group VIII in the catalyst in terms of oxide; the amount of the VIII group metal introduced into the catalyst from the step (4) accounts for 50-70% of the mass of the VIII group total metal oxide in the catalyst in terms of oxide.
9. The method according to claim 1, wherein in the step (4), the baking temperature is 600 to 900 ℃ and the baking time is controlled to 3 to 5 hours.
10. A residuum hydrogenation catalyst made by the process of any one of claims 1-9.
11. The catalyst according to claim 10, wherein the active metal is at least one of a group VIB metal and at least one of a group VIII metal, wherein the group VIB metal is preferably at least one of Mo, W, more preferably Mo, and the group VIII metal is preferably at least one of Co, ni, more preferably Ni.
12. The catalyst according to claim 10, wherein the catalyst comprises 10 to 30% of group VIB metal oxide, 2 to 15% of group VIII metal oxide and 8 to 20% of silica, based on the mass of the catalyst.
13. The catalyst according to claim 10, wherein the catalyst further comprises N, and the content of N is 0.5% to 1.0% in terms of simple substance based on the mass of the catalyst.
14. The catalyst of claim 10, wherein the catalyst has an active metal dispersity of: i VIB /I Al (. Times.100) is 3-10, I VIII /I Al (. Times.100) is 3 to 9.
15. The catalyst according to claim 10, characterized in that the specific surface area of the catalyst is 140-230 m 2 Preferably 170 to 200m 2 Per gram, the pore volume is 0.5-1.2 cm 3 Preferably 0.7 to 0.9cm per gram 3 And/g, the mechanical strength is 16-27N/mm, preferably 18-24N/mm, the pore volume of the pores with the pore diameter of 15-80 nm accounts for 6-23% of the total pore volume, preferably 10-14%, and the pore volume of the pores with the pore diameter of less than 8nm accounts for less than 8%, preferably 4-7% of the total pore volume.
16. Catalyst according to claim 10, characterized in that the acid amount of the catalyst is 0.4-0.9 mmol/g, preferably 0.6-0.8 mmol/g; ratio C of the amount of acid B to the amount of acid L B /C L 0.02 to 0.09, preferably 0.04 to 0.07.
17. Use of the catalyst of any one of claims 10-16 in a residuum hydrogenation process.
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