CN108940357B - Hydrodesulfurization catalyst of mesoporous ETS-10 zeolite carrier and preparation method and application thereof - Google Patents
Hydrodesulfurization catalyst of mesoporous ETS-10 zeolite carrier and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000010457 zeolite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 238000001035 drying Methods 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 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 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 22
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002791 soaking Methods 0.000 description 12
- 230000009257 reactivity Effects 0.000 description 7
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229910003294 NiMo Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000001174 ascending effect Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 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 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention provides a hydrodesulfurization catalyst of a mesoporous ETS-10 zeolite carrier, a preparation method and application thereofThe catalyst is prepared by loading at least two metal sulfides of Ni, Mo and W on mesoporous ETS-10 zeolite, wherein the specific surface area of the mesoporous ETS-10 zeolite is 250-420 m2The mesoporous volume is 0.1-0.21cm3(ii) in terms of/g. The invention utilizes the special pore channel structure of the mesoporous ETS-10 to load active metal on the ETS-10 zeolite, thereby synthesizing the hydrodesulfurization catalyst with high activity.
Description
Technical Field
The invention relates to a hydrodesulfurization catalyst of a mesoporous ETS-10 zeolite carrier and a preparation method and application thereof, in particular to a hydrodesulfurization catalyst taking high mesoporous ETS-10 zeolite as a carrier to load NiMo, NiW and NiMoW metal sulfides, and a preparation method and related application thereof, belonging to the fields of metal sulfide catalysts and preparation and application thereof.
Background
With the continuous decline of crude oil quality and the stricter environmental regulations around the world, countries around the world put forward new requirements on oil quality. National standards for automotive diesel oil (V) are implemented in 2018, 1 month and 1 day in China, and the sulfur content in fuel oil is definitely required to be less than 10ppm, and the content of polycyclic aromatic hydrocarbon is not higher than 11%. In order to obtain ultra-clean fuel and reduce the sulfur content in oil products, the most difficult-to-remove organic sulfur macromolecule 4, 6-dialkyl dibenzothiophene, such as 4, 6-dimethyl dibenzothiophene (4,6-DM-DBT), in the fuel fraction must be deeply removed.
Conventional addingThe hydrodesulfurization catalyst is, for example, described in CN107282053A as gamma-Al2O3The catalyst is a carrier-loaded CoMo, NiMo and NiW catalyst, but the hydrogenation activity is not high, so that the 4,6-DM-DBT in the fuel oil fraction is difficult to deeply remove under mild conditions (low temperature and low pressure).
In order to realize the production of ultra-clean oil products and deeply remove 4,6-DM-DBT, a high-efficiency and high-activity hydrodesulfurization catalyst must be prepared.
Disclosure of Invention
It is an object of the present invention to provide a hydrodesulfurization catalyst having high activity.
Another object of the present invention is to provide a method for preparing a hydrodesulfurization catalyst having high activity.
It is another object of the present invention to provide related applications of the high activity hydrodesulfurization catalyst.
On one hand, the invention provides a catalyst which is prepared by loading at least two metal sulfides of Ni, Mo and W on mesoporous ETS-10 zeolite, wherein the specific surface area of the mesoporous ETS-10 zeolite is 250-420 m2The mesoporous volume is 0.1-0.21cm3/g。
According to a specific embodiment of the present invention, in the catalyst of the present invention, in the supported metal sulfide, by weight percentage:
the load capacity of Mo in the metal Ni and Mo is 8-10% by mass of the carrier, and the atomic ratio of Ni to Mo is 0.3-0.4; or
The load capacity of W in the metal Ni and W is 10-15% by mass of the carrier, and the proportion of Ni atoms to Mo atoms is 0.4-0.5; or
The loading amounts of metal Ni, metal Mo and metal W in the loaded metal sulfide are respectively 2-4% and 4-8% by total mass of the carrier, and the atomic ratio of the metal Ni, the metal Mo and the metal W in the loaded metal sulfide is 0.1-0.8: 0.25-1: 1, preferably 0.4-0.8: 0.25-1: 1.
according to a specific embodiment of the present invention, in the catalyst of the present invention, the BET surface area of the mesoporous ETS-10 zeolite is 300-420m2Per g, the external surface area is 70-150m2Per g, the mesoporous volume is 0.1-0.21cm3G, pores of microporesThe volume is 0.08-0.14cm3/g。
According to a specific embodiment of the invention, in the catalyst of the invention, the mesoporous ETS-10 zeolite is mesoporous ETS-10 zeolite containing metal Ni and/or Co, and the content of Ni and/or Co is 1.5-3.0wt% of the mass of the zeolite.
According to an embodiment of the present invention, the mesoporous ETS-10 zeolite in the catalyst of the present invention may be a commercially available zeolite satisfying the requirements of the present invention, or may be prepared by itself according to the methods described in the prior art.
According to some embodiments of the present invention, the mesoporous ETS-10 zeolite may be synthesized according to the following method:
mixing water glass and NaOH aqueous solution, then sequentially adding KOH aqueous solution and titanium trichloride solution, uniformly stirring, finally adding aqueous solution containing metal nickel nitrate or cobalt nitrate, uniformly stirring, placing in a kettle, crystallizing at 230 ℃ for 72 hours, filtering, washing, drying, and calcining at high temperature to obtain white powder which is mesoporous ETS-10 zeolite. The gel composition of the synthetic mesoporous ETS-10 zeolite is SiO2：TiO2：Na2O：K2O：H2O: NiO is (6-7): 1: (3-5): (1-1.7): (150-200): (0.03-0.04).
According to other embodiments of the present invention, in the catalyst of the present invention, the mesoporous ETS-10 zeolite is preferably synthesized according to the following method:
1) mixing a silicon source with a NaOH solution to obtain a mixed solution, and adding Na in the mixed solution2O content 10.0-20.0 wt.%;
2) adding KOH or KF solution into the mixed solution in the step 1) to ensure that K is dissolved2The O content is 10.0-25.0 wt.%, and the mixture is stirred uniformly;
3) adding a titanium source solution into the mixed solution obtained in the step 2), and uniformly stirring;
4) adding a precursor compound containing metal Ni and/or Co into the mixed solution obtained in the step 3), and uniformly stirring;
5) performing crystallization reaction on the mixed solution obtained in the step 4) to obtain mesoporous ETS-10 zeolite (METS-10) containing metal.
In the above preferred method for synthesizing mesoporous ETS-10 zeolite, the silicon source may be water glass, and the composition thereof is as follows: SiO 22Na with the content of 5.2-6.0mol/L2O content of 1.3-2.0mol/L, H2The content of O is 45.0-50.0 mol/L. The titanium source may be titanium trichloride. The precursor compound containing metal Ni may be nickel nitrate hexahydrate, and the precursor compound containing metal Co may be cobalt nitrate hexahydrate.
In the preferable synthesis method of the mesoporous ETS-10 zeolite, the total amount of metal Ni and Co in a synthesis system can be controlled to be 1.5-3.0wt% of the mass of the zeolite, and the atomic weight ratio of the metal Ni to the metal Co is controlled to be 0-1: 1 or 1: 1-0.
In the preferable synthesis method of the mesoporous ETS-10 zeolite, the crystallization reaction condition is 200-250 ℃, and the crystallization reaction time is 20-110 hours; the optimized crystallization reaction condition is 200-230 ℃, and the crystallization reaction time is 72-110 hours.
In the preferred method for synthesizing the mesoporous ETS-10 zeolite, the molar ratio of the raw materials in the synthesis system is SiO2：TiO2：Na2O：K2O：H2O: NiO is (5-8): 1: (3-7): (0.5-2): (100-220): (0.02-0.05), wherein the mole number of the sodium oxide is the total of sodium elements contained in the silicon source water glass and the sodium hydroxide. Further preferred is SiO2：TiO2：Na2O：K2O：H2O: NiO is (6-7): 1: (3-5): (1-1.7): (150-200): (0.03-0.04).
According to the preferred method for synthesizing the mesoporous ETS-10 zeolite, the synthesized mesoporous ETS-10 zeolite containing the metal has a specific surface area of 320-420 m2The mesoporous volume is 0.11-0.21 cm3(ii) in terms of/g. Furthermore, the pore volume of the micropores is 0.10-0.13 cm3/g。
In another aspect, the present invention also provides a method for preparing the catalyst, comprising the steps of:
(1) dissolving the metal Ni, Mo or the metal Ni, W or the metal salt of the metal Ni, Mo, W in an aqueous solution;
(2) and (2) impregnating the mesoporous ETS-10 zeolite carrier with aqueous solution of metal salt, drying and calcining the mesoporous ETS-10 zeolite impregnated with the aqueous solution to obtain the catalyst.
According to a particular embodiment of the invention, the process for preparing the catalyst of the invention further comprises:
(3) putting the catalyst obtained by drying and calcining in the step (2) into H2S/H2Sulfurizing in mixed gas atmosphere or with CS2And carrying out liquid-phase vulcanization to obtain the vulcanized hydrodesulfurization catalyst.
According to a specific embodiment of the present invention, in the method for preparing the catalyst of the present invention, in the step (1), the metal salt of Mo is (NH)4)6Mo7O24·4H2O; the metal salt of Ni is Ni (NO)3)2·6H2O、NiCO3·2Ni(OH)2·4H2O; w salt is (NH)4)6W7O24·4H2O。
According to a specific embodiment of the present invention, the catalyst of the present invention is prepared by a method in which, in step (3), the sulfidation conditions are: starting from room temperature, increasing the temperature to 400-450 ℃ at the rising speed of 2-5 ℃/min, keeping the temperature for 3-5 hours, and obtaining the H2S/H2H in the mixed gas2S is 10-25 vol%.
In another aspect, the invention also provides the use of the catalyst as a catalyst for hydrodesulfurization reactions.
In the specific application, the hydrodesulfurization reaction conditions are as follows: the reaction temperature is 280-380 ℃, the hydrogen partial pressure is 6.0-9.0 MPa, the hydrogen-oil volume ratio is 300: 1-600: 1, and the volume airspeed is 0.5-3.0 h-1。
Compared with the prior art, the invention has the beneficial effects that:
the invention uses porous ETS-10 zeolite as a carrier, takes NiMo, NiW and NiMoW as active components, prepares a novel hydrodesulfurization catalyst with desulfurization activity far higher than that of the traditional catalyst by an impregnation method, and solves the problem that the traditional metal sulfide catalyst can not remove 4,6-DM-DBT under mild conditions.
Drawings
FIG. 1 is a graph comparing the reactivity of the catalysts of example 1 and comparative example 1 to 4, 6-DMDBT.
FIG. 2 is a comparison of the reactivity of example 3 and comparative example 3 catalysts to 4, 6-DMDBT.
FIG. 3 is a comparison of the reactivity of example 5 and comparative example 5 catalysts to 4, 6-DMDBT.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The mesoporous ETS-10 zeolite used in each example was the same and had a BET surface area of 378m2Per g, external surface area of 90m2Per g, the mesoporous volume is 0.21cm3Per g, pore volume of the micropores was 0.11cm3/g。
Example 1
0.2944g (NH)4)6Mo7O24·4H2O、0.1942g Ni(NO3)2·6H2Dissolving O in 2.0g water, dripping into 2g porous ETS-10(ETS-10-M) powder, soaking, naturally drying, oven drying at 100 deg.C for 20 hr, and adding 10 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours in an atmosphere of hydrogen gas of S at an ascending rate of 3 ℃/min. The supported amount of Mo was 8.0%/(g. ETS-10-M) based on the mass of ETS-10-M, and the atomic ratio of Ni/Mo was 0.3.
Example 2
0.3680g (NH)4)6Mo7O24·4H2O and 0.2427g Ni (NO)3)2·6H2Dissolving O in 2.0g water, dripping into 2g ETS-10-M powder after dissolving completely, naturally drying after soaking, drying in oven at 100 deg.C for 20 hr, and finally adding 10 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours in an atmosphere of hydrogen gas of S at an ascending rate of 3 ℃/min. The supported amount of Mo was 10.0%/(g. ETS-10-M) based on the mass of ETS-10-M, and the atomic ratio of Ni/Mo was 0.4.
Example 3
0.4400g (NH)4)6W7O24·6H2O and 0.2375g Ni (NO)3)2·6H2Dissolving O in 2.0g water, dripping into 2g ETS-10-M powder, soaking, naturally drying, drying in oven at 100 deg.C for 20 hr, and drying in oven containing 15% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The supported amount of W was 15%/(g. ETS-10-M) based on the mass of ETS-10-M, and the atomic ratio of Ni/W was 0.5.
Example 4
0.2933g (NH)4)6W7O24·6H2O and 0.1267g Ni (NO)3)2·6H2Dissolving O in 2.0g water, dripping into 2g ETS-10-M powder, soaking, naturally drying, drying in oven at 100 deg.C for 20 hr, and drying in oven containing 15% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The supported amount of W was 10%/(g. ETS-10-M) based on the mass of ETS-10-M, and the atomic ratio of Ni/W was 0.4.
Example 5
0.1173g (NH)4)6W7O24·6H2O and 0.0507g Ni (NO)3)2·6H2O and 0.0736g (NH)4)6Mo7O24·4H2Dissolving O in 2.0g water, dripping into 2g ETS-10-M powder after dissolving completely, naturally drying after soaking, drying in oven at 100 deg.C for 20 hr, and finally adding 20 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The Mo loading was 2%/(g. ETS-10-M) by mass of ETS-10-M, the W loading was 4%/(g. ETS-10-M) by mass of ETS-10-M, and the atomic ratio of Ni/Mo/W was 0.4/1/1.
Example 6
0.2346g (NH)4)6W7O24·6H2O and 0.1014g Ni (NO)3)2·6H2O and 0.1472g (NH)4)6Mo7O24·4H2Dissolving O in 2.0g water, dripping into 2g ETS-10-M powder, soaking, naturally drying, and oven drying at 100 deg.CDried for 20H, and finally, the solution is dried in the presence of 20 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The Mo loading was 4%/(g. ETS-10-M) by mass of ETS-10-M, the W loading was 8%/(g. ETS-10-M) by mass of ETS-10-M, and the atomic ratio of Ni/Mo/W was 0.4/1/1.
Comparative example 1
0.2944g (NH)4)6Mo7O24·4H2O、0.1942g Ni(NO3)2·6H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking the powder in water, naturally drying, drying in 100 deg.C oven for 20 hr, and adding 10 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours in an atmosphere of hydrogen gas of S at an ascending rate of 3 ℃/min. The loading amount of Mo is gamma-Al2O38.0%/(g. gamma. -Al) by mass2O3) The Ni/Mo atomic ratio was 0.3.
Comparative example 2
0.3680g (NH)4)6Mo7O24·4H2O and 0.2427g Ni (NO)3)2·6H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking the powder in water, naturally drying, drying in 100 deg.C oven for 20 hr, and adding 10 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours in an atmosphere of hydrogen gas of S at an ascending rate of 3 ℃/min. The loading amount of Mo is gamma-Al2O310.0%/(g. gamma. -Al) by mass2O3) The Ni/Mo atomic ratio was 0.4.
Comparative example 3
0.4400g (NH)4)6W7O24·6H2O and 0.2375g Ni (NO)3)2·6H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking in the powder, naturally drying, drying in oven at 100 deg.C for 20 hr, and adding 15% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The amount of W supported is gamma-Al2O3Mass is 15%/(g. gamma. -Al)2O3) The atomic ratio of Ni/W was 0.5.
Comparative example 4
0.2933g (NH)4)6W7O24·6H2O and 0.1267g Ni (NO)3)2·6H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking in the powder, naturally drying, drying in oven at 100 deg.C for 20 hr, and adding 15% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The amount of W supported is gamma-Al2O310%/(g. gamma. -Al) by mass2O3) The atomic ratio of Ni/W was 0.4.
Comparative example 5
0.1173g (NH)4)6W7O24·6H2O and 0.0507g Ni (NO)3)2·6H2O and 0.0736g (NH)4)6Mo7O24·4H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking in powder, naturally drying, drying in oven at 100 deg.C for 20 hr, and adding 20 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. The Mo loading is 2%/(g. gamma. -Al) based on the mass of ETS-10-M2O3) W in the amount of gamma-Al2O34%/(g. gamma. -Al) by mass2O3) The atomic ratio of Ni/Mo/W was 0.4/1/1.
Comparative example 6
0.2346g (NH)4)6W7O24·6H2O and 0.1014g Ni (NO)3)2·6H2O and 0.1472g (NH)4)6Mo7O24·4H2O was dissolved in 1.6g of water, and after all dissolved, 2g of gamma-Al was added dropwise2O3Soaking in powder, naturally drying, drying in oven at 100 deg.C for 20 hr, and adding 20 vol.% H2And (3) vulcanizing at 450 ℃ for 4 hours at a rising speed of 3 ℃/min in a hydrogen atmosphere of S. Supported by Mo in gamma-Al2O3Mass is 4%/(g. gamma. -A)l2O3) The supported amount of W was 8%/(g. gamma. -Al) based on the mass of ETS-10-M2O3) The atomic ratio of Ni/Mo/W was 0.4/1/1.
The activity of the catalyst obtained above was evaluated by catalytic hydrodesulfurization reaction as follows.
Hydrodesulfurization reaction conditions: the reaction is carried out on a stainless steel fixed bed reactor, the loading of the vulcanized catalyst is 0.4g, 4,6-DM-DBT is dissolved in decahydronaphthalene solution, the mass percentage content of 4,6-DM-DBT is 1.0 percent, the reaction mixture is conveyed to the reactor by a metering pump, the reaction temperature is 280 ℃, the hydrogen pressure is 5.0MPa, and H is2700/oil, weight hourly space velocity of 14h-1。
TABLE 1 evaluation of the reactivity of the catalysts obtained in the different examples and comparative examples
| Examples | Conversion of 4, 6-dimethyldibenzothiophene% |
| Example 1 | 80 |
| Example 2 | 84 |
| Example 3 | 79 |
| Example 4 | 93 |
| Example 5 | 91 |
| Example 6 | 90 |
| Comparative example 1 | 60 |
| Comparative example 2 | 62 |
| Comparative example 3 | 61 |
| Comparative example 4 | 67 |
| Comparative example 5 | 63 |
| Comparative example 6 | 62 |
Note: the reaction time was 48 h.
As can be seen from Table 1, the hydrodesulfurization activity of the mesoporous ETS-10 zeolite supported metal sulfide catalyst was higher than that of the alumina supported metal sulfide catalyst.
FIG. 1 is a graph comparing the reactivity of the catalysts of example 1 and comparative example 1 to 4, 6-DMDBT.
FIG. 2 is a comparison of the reactivity of example 3 and comparative example 3 catalysts to 4, 6-DMDBT.
FIG. 3 is a comparison of the reactivity of example 5 and comparative example 5 catalysts to 4, 6-DMDBT.
As can be seen from FIG. 1, the hydrodesulfurization activity of the NiMo/ETS-10-M catalyst of example 1 is much higher than that of the NiMo/γ -Al catalyst of comparative example 12O3A catalyst. FIG. 2 shows that the conversion of 4,6-DMDBT over the NiW/ETS-10-M catalyst of example 3 is higher than that of NiW/gamma-Al of comparative example 32O3A catalyst. FIG. 3 shows that the hydrodesulfurization activity of the catalyst of example 5(NiMoW/ETS-10-M) is also much higher than that of the catalyst of comparative example 5 (NiMoW/gamma-Al)2O3) A catalyst. As can be seen by comparing FIGS. 1, 2 and 3, the NiMoW/ETS-10-M catalyst of example 5 has a higher hydrodesulfurization activity than the catalysts of examples 1 and 3.
Claims (10)
1. A hydrodesulfurization catalyst is prepared by loading at least two metal sulfides of Ni, Mo and W on mesoporous ETS-10 zeolite, wherein the specific surface area of the mesoporous ETS-10 zeolite is 250-420 m2The mesoporous volume is 0.1-0.21cm3/g；
Wherein, by weight percentage, the metal sulfide is loaded:
the load capacity of Mo in the metal Ni and Mo is 8-10% by mass of the carrier, and the atomic ratio of Ni to Mo is 0.3-0.4; or
The load capacity of W in the metal Ni and W is 10-15% by mass of the carrier, and the proportion of Ni atoms to Mo atoms is 0.4-0.5; or
The loading amounts of metal Ni, metal Mo and metal W in the loaded metal sulfide are respectively 2-4% and 4-8% by total mass of the carrier, and the atomic ratio of the metal Ni, the metal Mo and the metal W in the loaded metal sulfide is 0.1-0.8: 0.25-1: 1; the mesoporous ETS-10 zeolite is synthesized by the following method:
mixing water glass and NaOH aqueous solution, sequentially adding KOH aqueous solution and titanium trichloride solution, uniformly stirring, adding aqueous solution containing metal nickel nitrate or cobalt nitrate, uniformly stirring, placing in a kettle, crystallizing at 230 ℃ for 72 hours, filtering, washing, drying, and calcining at high temperature to obtain white powder which is mesoporous ETS-10 zeolite; the gel composition of the mesoporous ETS-10 zeolite is SiO2：TiO2：Na2O：K2O：H2O: NiO is (6-7): 1: (3-5): (1-1.7): (150-200): (0.03-0.04).
2. The hydrodesulfurization catalyst according to claim 1, wherein the loading amounts of the metals Ni, Mo and W in the supported metal sulfide are respectively 2-4% and 4-8% by total mass of the support, and the atomic ratio of Ni, Mo and W in the supported metal sulfide is 0.4-0.8: 0.25-1: 1.
3. the hydrodesulfurization catalyst as recited in claim 1 wherein said mesoporous ETS-10 zeolite has a BET surface area of 300-420m2Per g, the external surface area is 70-150m2Per g, the mesoporous volume is 0.1-0.21cm3Per g, the pore volume of the micropores is 0.08-0.14cm3/g。
4. The hydrodesulfurization catalyst of claim 1 wherein the mesoporous ETS-10 zeolite is a mesoporous ETS-10 zeolite containing metal Ni or Co in an amount of 1.5-3.0wt% of the zeolite mass.
5. A process for preparing a hydrodesulfurization catalyst as claimed in any one of claims 1 to 4, which comprises the steps of:
(1) dissolving the metal Ni, Mo or the metal Ni, W or the metal salt of the metal Ni, Mo, W in an aqueous solution;
(2) and (2) impregnating the mesoporous ETS-10 zeolite carrier with a metal salt aqueous solution, drying and calcining the mesoporous ETS-10 zeolite impregnated with the solution to obtain the hydrodesulfurization catalyst.
6. The method of claim 5, further comprising:
(3) putting the catalyst obtained by drying and calcining in the step (2) into H2S/H2Sulfurizing in mixed gas atmosphere or with CS2And carrying out liquid-phase vulcanization to obtain the vulcanized hydrodesulfurization catalyst.
7. The method according to claim 5, wherein in the step (1), the metal salt of Mo is (NH)4)6Mo7O24·4H2O; the metal salt of Ni is Ni (NO)3)2·6H2O、NiCO3∙2Ni(OH)2∙4H2O; w salt is (NH)4)6W7O24·4H2O。
8. The method according to claim 6, wherein in step (3), the vulcanization conditions are: starting from room temperature, increasing the temperature to 400-450 ℃ at the rising speed of 2-5 ℃/min, keeping the temperature for 3-5 hours, and obtaining the H2S/H2H in the mixed gas2S is 10-25 vol%.
9. Use of a hydrodesulfurization catalyst according to any one of claims 1 to 4 in a hydrodesulfurization reaction.
10. The use according to claim 9, wherein the hydrodesulfurization reaction conditions are: the reaction temperature is 280-380 ℃, the hydrogen partial pressure is 6.0-9.0 MPa, the hydrogen-oil volume ratio is 300: 1-600: 1, and the volume airspeed is 0.5-3.0 h-1。
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