CN117138825A - Hydrodesulfurization catalyst and preparation method and application thereof - Google Patents
Hydrodesulfurization catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000005342 ion exchange Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 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 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 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 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000002149 hierarchical pore Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- 239000008367 deionised water Substances 0.000 description 37
- 229910021641 deionized water Inorganic materials 0.000 description 37
- 238000002791 soaking Methods 0.000 description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 229910003296 Ni-Mo Inorganic materials 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001802 infusion Methods 0.000 description 7
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000011280 coal tar Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The application discloses a hydrodesulfurization catalyst and a preparation method and application thereof, wherein the catalyst comprises the following components: an active component, an auxiliary component and a carrier; the carrier is Meso-USY-Al 2 O 3 A carrier; the active component is Mo; the auxiliary agent component is Ni or Co; wherein the Meso-USY-Al 2 O 3 The carrier is a hierarchical pore Y molecular sieve and gamma-Al 2 O 3 Is a complex carrier of (a) and (b). The carrier is a multi-stage mesoporous Y molecular sieve and gamma-Al 2 O 3 The composite carrier of the catalyst has a mesoporous structure and large specific surface area, and can improve the performance of the hydrodesulfurization catalyst.
Description
Technical Field
The application relates to the technical field of coal chemical industry, in particular to a hydrodesulfurization catalyst and a preparation method and application thereof.
Background
The coal tar hydrofining process mainly comprises the reaction processes of hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrocracking and the like. The sulfur content in fuel oil is one of the important indexes for measuring the quality of oil products. The sulfur-containing compounds in the oil products can generate a large amount of sulfur-containing gas after being combusted, and pollute the environment. According to the latest emission standards of national clean gasoline and diesel oil and aviation kerosene, it is required to reduce the sulfur content in oil products to a level of 10ppm or less.
In recent years, the yield of coal tar rises year by year, the sulfur content in the coal tar is higher and higher, and the removal of sulfur compounds such as dibenzothiophene and alkyl substitutes thereof from the coal tar is attracting attention. Desulfurization methods can be classified into conventional hydrodesulfurization and non-hydrodesulfurization, and hydrodesulfurization techniques are widely used, and the catalytic activity of the catalyst is extremely important in this technique.
The dibenzothiophene compound accounts for a high proportion in the total amount of sulfur-containing compounds in the medium-low temperature coal tar. The removal of sulfur from fuel oils is achieved primarily by Hydrodesulfurization (HDS) using transition metal sulfide (CoMo and NiMo) catalysts. However, the organic sulfur-containing compounds in coal tar have complex multi-aromatic ring structures, high C-S bond energy and difficult fracture, and particularly have steric hindrance effect of methyl substituent groups of benzene rings close to sulfur atoms in 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT), so that the fracture of the C-S bond is inhibited, and complete desulfurization is difficult on the traditional transition metal sulfur-state catalyst. To obtain ultra-low sulfur fuel oil meeting national standards, it is necessary to prepare a highly efficient, high activity hydrodesulfurization catalyst.
Disclosure of Invention
In order to solve the above-mentioned shortcomings in the art, the present application aims to provide a hydrodesulfurization catalyst and a preparation method and application thereof.
According to an aspect of the present application, there is provided a hydrodesulfurization catalyst comprising: an active component, an auxiliary component and a carrier;
the carrier is Meso-USY-Al 2 O 3 A carrier;
the active component is Mo;
the auxiliary component is one or two selected from Ni and Co;
wherein the Meso-USY-Al 2 O 3 The carrier is a multi-stage mesoporous Y molecular sieve and gamma-Al 2 O 3 Is a complex carrier of (a) and (b).
According to some embodiments of the application, the active component is 9-13wt%.
According to some embodiments of the application, the auxiliary agent is 2-5wt%.
According to another aspect of the present application, there is provided a method for preparing a hydrodesulfurization catalyst comprising:
by NaAlO 2 And Na (Na) 2 SiO 3 ·9H 2 O is used for preparing a guiding agent;
mixing the guiding agent with a TPHAC template agent, an aluminum sulfate solution and a KOH solution, and reacting in a polytetrafluoroethylene hydrothermal synthesis kettle to obtain a Y molecular sieve;
combining the Y molecular sieve with (NH) 4 ) 2 SO 4 Sequentially carrying out primary ion exchange, hydrothermal treatment and secondary ion exchange on the solution, and carrying out multi-stage mesoporous Y molecular sieve;
gamma-Al 2 O 3 Preparing Meso-USY-Al with the multilevel mesoporous Y molecular sieve by adopting a sol-gel method 2 O 3 A carrier;
the Meso-USY-Al is modified and impregnated 2 O 3 And loading active components on the carrier to obtain the hydrodesulfurization catalyst.
According to some embodiments of the application, a modified impregnation method is used in the Meso-USY-Al 2 O 3 Load on the carrierThe active components are used for obtaining the hydrodesulfurization catalyst, which comprises the following components:
dissolving an auxiliary agent and a chelating agent in water to form a first impregnating solution;
dissolving a Mo metal precursor in water to form a second impregnating solution;
subjecting the Meso-USY-Al 2 O 3 And (3) immersing the carrier in the second impregnating solution, drying, immersing in the first impregnating solution, drying again, and roasting to obtain the hydrodesulfurization catalyst.
According to some embodiments of the application, gamma-Al is 2 O 3 Preparing Meso-USY-Al with the multilevel mesoporous Y molecular sieve by adopting a sol-gel method 2 O 3 The carrier comprises:
gamma-Al 2 O 3 Mixing with water, regulating pH to 1-3, adding the multi-stage mesoporous Y molecular sieve, maintaining pH of the system unchanged, stirring for 4-8 hr, regulating pH to 8-10, standing for aging for 2-5 hr, washing, drying, and roasting to obtain the final product 2 O 3 A carrier;
according to some embodiments of the application, optionally, the step of adding gamma-Al 2 O 3 Mixing with water, and adjusting the pH of the solution to 1.
According to some embodiments of the application, the chelating agent is selected from: ethylenediamine tetraacetic acid.
According to a further aspect of the present application there is provided the use of a hydrodesulphurisation catalyst in the hydrodesulphurisation of 4, 6-dimethyldibenzothiophene.
According to an aspect of the present application, there is provided a multi-stage mesoporous molecular sieve prepared by a method comprising:
by NaAlO 2 And Na (Na) 2 SiO 3 ·9H 2 O is used for preparing a guiding agent;
mixing the guiding agent with a TPHAC template agent, an aluminum sulfate solution and a KOH solution, and reacting in a polytetrafluoroethylene hydrothermal synthesis kettle to obtain a Y molecular sieve;
combining the Y molecular sieve with (NH) 4 ) 2 SO 4 Sequentially performing ion exchange, hydrothermal treatment and ion exchange twice on the solution to obtain the multi-functional ion exchange membraneA hierarchical mesoporous Y molecular sieve.
The application of the multi-level mesoporous molecular sieve in preparing the 4, 6-dimethyl dibenzothiophene hydrodesulfurization catalyst.
Compared with the prior art, the application at least has the following beneficial effects:
the application provides a hydrodesulfurization catalyst, which uses the Meso-USY-Al provided by the application 2 O 3 The carrier is used as a carrier, and the carrier is a multi-stage mesoporous Y molecular sieve and gamma-Al 2 O 3 The composite carrier of the catalyst has a mesoporous structure and large specific surface area, and can improve the performance of the hydrodesulfurization catalyst.
The multistage mesoporous Y molecular sieve adopts an inexpensive soft template agent, and adopts a hydrothermal synthesis method, and the synthesis method is simple and easy to operate and low in cost. The molecular sieve prepared by the method has higher specific surface area and pore volume and good hydrothermal stability.
The Meso-USY-Al 2 O 3 The carrier is coupled with the multilevel mesoporous Y molecular sieve and gamma-Al by a sol-gel method 2 O 3 The composite carrier is prepared, the components of the carrier prepared by the synthetic method are uniformly distributed, and the mesoporous structure introduced into the carrier is beneficial to the diffusion of 4, 6-DMDBT.
The application adopts a modified dipping method in Meso-USY-Al 2 O 3 The active metal component is loaded on the carrier, and the chelating agent is added in the loading step, so that the auxiliary metal precursor preferentially acts with the chelating agent to generate chelate, the vulcanization temperature of the auxiliary metal is improved, the formation of Co (Ni) -Mo-S (II) active centers is facilitated, and the catalytic hydrodesulfurization activity is remarkably improved.
In the hydrodesulfurization catalyst, gamma-Al can be weakened through modification of the multi-stage mesoporous Y molecular sieve 2 O 3 The interaction between the carrier and the active metal component forms more Co (Ni) -Mo-S (II) active species, and finally the high-performance 4,6-DMDBT removal catalyst is obtained.
Drawings
FIG. 1 is a comparison of the reaction properties of 4, 6-dimethyldibenzothiophene of the catalysts of example 2 and comparative example 1, comparative example 2.
FIG. 2 is a comparison of the reaction properties of 4, 6-dimethyldibenzothiophene for the catalysts of example 5 and comparative example 3.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It is particularly pointed out that similar substitutions and modifications to the application will be apparent to those skilled in the art, which are all deemed to be included in the application. It will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, or in the appropriate variations and combinations, without departing from the spirit and scope of the application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application.
The application is carried out according to the conventional conditions or the conditions suggested by manufacturers if the specific conditions are not noted, and the raw materials or auxiliary materials and the reagents or instruments are conventional products which can be obtained commercially if the manufacturers are not noted.
The present application will be described in detail below.
Conventional hydrodesulfurization catalysts are commercially available as gamma-Al 2 O 3 A metal catalyst which is a carrier and is loaded with Co (Ni) Mo active components. However, due to gamma-Al 2 O 3 The strong interaction between the support and the active metal component makes the catalyst difficult to be completely vulcanized during vulcanization, and the formed Co (Ni) -Mo-S (II) has small number of active species and low hydrodesulfurization activity. In addition, 4,6-DMDBT has high steric hindrance effect, so that the 4,6-DMDBT has high steric hindrance effect on microporous gamma-Al 2 O 3 Diffusion on the support is difficult, the reaction rate is slow, and further lower hydrodesulfurization activity is caused.
The application utilizes a cheap soft template agent and adopts a simple hydrothermal synthesis method to prepare the multistage pore superstable USY molecular sieve, whichThe multi-stage pore structure is beneficial to the diffusion of reactants and products. Coupling of high specific surface area commercial gamma-Al by sol-gel process 2 O 3 Preparation of composite Meso-USY-Al 2 O 3 The carrier is improved by the traditional dipping mode, chelating agent is added, and different active metal components are loaded on the Meso-USY-Al 2 O 3 And (3) on a carrier.
The catalyst with mesoporous structure and large specific surface area for improving the hydrodesulfurization reaction performance of 4,6-DMDBT mainly comprises an active component, an auxiliary agent and a carrier. The active component is Mo metal, the auxiliary component is Ni, co, etc., and the carrier is Meso-USY-Al 2 O 3 。
Active component loading: 2-5wt% Ni (Co), 9-13wt% Mo.
The preparation method of the hydrodesulfurization catalyst comprises the following steps:
1. synthesis of multistage mesoporous Y molecular sieve (Meso-USY molecular sieve)
Weighing a certain amount of NaAlO 2 And Na (Na) 2 SiO 3 ·9H 2 O is dissolved in a proper amount of deionized water, stirred and mixed uniformly, and kept stand and aged for 12-24 hours at 20-40 ℃ to obtain white gel, and the gel is named as a guiding agent;
weighing a proper amount of guiding agent, adding a proper amount of TPHAC template agent, aluminum sulfate solution, KOH solution and deionized water, fully stirring, transferring the obtained mixed solution to a polytetrafluoroethylene hydrothermal synthesis kettle, and crystallizing at 80-150 ℃;
washing the crystallized product with deionized water, drying, and roasting at high temperature to remove the template agent to obtain a Y molecular sieve;
weighing a proper amount of Y molecular sieve and a certain concentration of (NH) 4 ) 2 SO 4 Ion exchange is carried out on the solution, and steam assisted hydrothermal treatment is carried out for 1-3h at 550-650 ℃;
reuse (NH) 4 ) 2 SO 4 And carrying out ion exchange on the solution for the second time, washing, drying and roasting to remove the template agent, thus obtaining the multi-stage mesoporous Y molecular sieve (Meso-USY molecular sieve).
2. Preparation of Meso-USY-Al by sol-gel method 2 O 3 Composite materialCarrier body
Weighing gamma-Al with high specific surface area 2 O 3 Mixing with deionized water, stirring, placing in 60-80deg.C oil bath, and adjusting pH to 1-3 with dilute nitric acid;
adding a Meso-USY molecular sieve, supplementing a proper amount of dilute nitric acid during the process to maintain the pH of the system to be basically unchanged, and continuously stirring for 4-8 hours;
regulating the pH of the system to 8-10 by adopting ammonia water, standing and ageing for 2-5h;
washing the carrier with deionized water, suction filtering to neutrality, drying, and calcining at 500-600deg.C.
The preparation can be carried out by regulating and controlling gamma-Al 2 O 3 And the Meso-USY addition amount to obtain Meso-USY-Al with different mass fractions 2 O 3 A carrier.
3. Modified impregnation method for loading active components
Weighing a proper amount of auxiliary metal precursor and ethylenediamine tetraacetic acid chelating agent, wherein the molar ratio of the auxiliary metal precursor to the ethylenediamine tetraacetic acid chelating agent is between 0.9 and 1.1, and dissolving the auxiliary metal precursor and the ethylenediamine tetraacetic acid chelating agent in deionized water to form an impregnating solution A;
weighing Mo metal precursor and dissolving in ionized water to form impregnating solution B;
first, meso-USY-Al is used 2 O 3 The carrier is immersed in the immersion liquid B, dried, immersed in the immersion liquid A again, dried and roasted to obtain the hydrodesulfurization catalyst, wherein the immersion is carried out for 6 hours and the drying is carried out for 12 hours.
Commercial high specific surface area gamma-Al used in the examples of the present application 2 O 3 The catalyst is purchased from Shandong Huajian aluminum products group Co., ltd, with the specification of 381.6m 2 Other brands of gamma-Al with high specific surface area 2 O 3 And can also be used in the present application.
Example 1 preparation of a Multi-stage mesoporous Y molecular sieve (Meso-USY molecular sieve)
Weigh 3.16g NaAlO 2 And 4.43g Na 2 SiO 3 ·9H 2 O is dissolved in deionized water, stirred and mixed uniformly, and kept stand and aged for 16 hours at 35 ℃ to obtain white gel; 33.92g of Na was added 2 SiO 3 ·9H 2 O,3.4g TPHAC template, 5.79g silica sol3.02g KOH and 121.43mL deionized water, fully stirring, transferring the mixed solution to a polytetrafluoroethylene hydrothermal synthesis kettle, crystallizing for 48 hours at 100 ℃, washing with deionized water, drying, roasting at high temperature, and removing a template agent to obtain the Y molecular sieve.
5g of the Y molecular sieve prepared in example 1 are weighed with 1mol/L (NH 4 ) 2 SO 4 Ion exchange of the solution, steam assisted hydrothermal treatment at 600deg.C for 2h, and (NH) 4 ) 2 SO 4 Carrying out ion exchange on the solution for 2 times, washing and drying; roasting for 2h at 550 ℃ to obtain the multi-stage mesoporous Y molecular sieve.
The specific surface area was measured to be 652m 2 /g, mesoporous specific surface area of 135m 2 And/g, the size of the intragranular mesopores is 3.9nm.
Example 2 preparation of hydrodesulfurization catalyst Using Multi-stage mesoporous Y molecular sieves (Meso-USY molecular sieves) as Supports
0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B.
5g of the multistage mesoporous Y molecular sieve carrier is firstly immersed in the solution B, dried, then immersed in the immersion liquid A, finally dried and roasted to obtain the Ni-Mo/Meso-USY catalyst.
Example 3
Preparation of Meso-USY-Al 2 O 3 And (3) a carrier: 1g of gamma-Al is weighed 2 O 3 Adding deionized water, stirring, mixing, and standing at 70deg.C in oil bath pan; adjusting the pH value of the solution to 1 by adopting dilute nitric acid; adding 4g of the Meso-USY molecular sieve prepared in the example 1, supplementing a proper amount of dilute nitric acid during the period to maintain the pH of the system basically unchanged, and continuously stirring for 6 hours; regulating the pH value of the system to 9 by adopting ammonia water, standing and ageing for 3 hours; washing the catalyst with deionized water, suction filtering to neutrality, drying, and roasting to obtain 80Meso-USY-Al 2 O 3 And (3) a composite carrier.
The carrier carries the active components: 0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. 5g of 80Meso-USY-Al 2 O 3 Soaking the composite carrier in the soaking solution B, drying, soaking in the soaking solution A, drying, and roasting to obtain Ni-Mo/80Meso-USY-Al 2 O 3 A catalyst.
Example 4
Preparation of Meso-USY-Al 2 O 3 And (3) a carrier: 2g of gamma-Al is weighed 2 O 3 And deionized water are stirred and mixed uniformly and placed in an oil bath at the constant temperature of 70 ℃. The pH of the solution was adjusted to 1 with dilute nitric acid, 3g of the Meso-USY molecular sieve prepared in example 1 was added, and during this period, an appropriate amount of dilute nitric acid was added to maintain the pH of the system substantially unchanged, and stirring was continued for 6 hours. Then ammonia water is adopted to adjust the pH value of the system to 9, standing and aging are carried out for 3 hours, deionized water is used for washing, suction filtration is carried out to neutrality, and 60Meso-USY-Al is obtained after drying and roasting 2 O 3 A carrier.
The carrier carries the active components: 0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. Subsequently, 5g of 60Meso-USY-Al were used 2 O 3 Soaking the carrier in soaking solution B, drying, soaking in soaking solution A, drying, and roasting to obtain Ni-Mo/60Meso-USY-Al 2 O 3 A catalyst.
Example 5
Preparation of Meso-USY-Al 2 O 3 And (3) a carrier: 3g of gamma-Al is weighed 2 O 3 And deionized water are stirred and mixed uniformly and placed in an oil bath at the constant temperature of 70 ℃. The pH of the solution was adjusted to 1 with dilute nitric acid, and 2g of the Meso-USY molecular sieve prepared in example 1 was added, during which time the pH of the system was maintained substantially constant by supplementing an appropriate amount of dilute nitric acid, and stirring was continued for 6 hours. Then ammonia water is adopted to adjust the pH value of the system to 9, and the system is stood for aging for 3 hours, and deionizedWashing with water, suction filtering to neutrality, drying, and calcining to obtain 40Meso-USY-Al 2 O 3 A carrier.
The carrier carries the active components: 0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. Subsequently, the B solution was first immersed in 5g of 40Meso-USY-Al 2 O 3 Drying the carrier, loading the active metal of the A impregnation liquid on the carrier, and finally drying and roasting to obtain Ni-Mo/40Meso-USY-Al 2 O 3 A catalyst.
Example 6
Preparation of Meso-USY-Al 2 O 3 And (3) a carrier: weigh 4g of gamma-Al 2 O 3 And deionized water are stirred and mixed uniformly and placed in an oil bath at the constant temperature of 70 ℃. The pH of the solution was adjusted to 1 with dilute nitric acid, 1g of the Meso-USY molecular sieve prepared in example 1 was added, and during this period, an appropriate amount of dilute nitric acid was added to maintain the pH of the system substantially unchanged, and stirring was continued for 6 hours. Then ammonia water is adopted to adjust the pH value of the system to 9, standing and aging are carried out for 3 hours, deionized water is used for washing, suction filtration is carried out to neutrality, and 20Meso-USY-Al is obtained after drying and roasting 2 O 3 A carrier.
The carrier carries the active components: 0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. Subsequently, 5g of 20Meso-USY-Al were first of all added 2 O 3 Soaking the carrier in soaking solution B, drying, soaking in soaking solution A, drying, and roasting to obtain Ni-Mo/20Meso-USY-Al 2 O 3 A catalyst.
Example 7
Preparation of Meso-USY-Al 2 O 3 And (3) a carrier: 3g of gamma-Al is weighed 2 O 3 And deionized water are stirred and mixed uniformly and placed in an oil bath at the constant temperature of 70 ℃. By usingThe pH of the solution was adjusted to 1 with dilute nitric acid, and 2g of the Meso-USY molecular sieve prepared in example 1 was added, during which time the pH of the system was maintained substantially constant with the addition of an appropriate amount of dilute nitric acid, and stirring was continued for 6 hours. Then ammonia water is adopted to adjust the pH value of the system to 9, standing and aging are carried out for 3 hours, deionized water is used for washing, suction filtration is carried out to neutrality, and 40Meso-USY-Al is obtained after drying and roasting 2 O 3 A carrier.
The carrier carries the active components: 0.87g of Co (NO) was weighed out 3 ) 3 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. Subsequently, 5g of 40Meso-USY-Al were first of all added 2 O 3 Soaking the carrier in soaking solution B, drying, soaking in soaking solution A, drying, and roasting to obtain Co-Mo/40Meso-USY-Al 2 O 3 A catalyst.
Comparative example 1 with gamma-Al 2 O 3 Is a carrier
0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent are dissolved in 5mL of deionized water to form an impregnating solution A; 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 5mL of deionized water to form impregnating solution B;
first, 5g of gamma-Al is added 2 O 3 Soaking the carrier in solution B, drying, soaking in soaking solution A, drying, and roasting to obtain Ni-Mo/Al 2 O 3 A catalyst.
Comparative example 2 commercial Y molecular sieves were used as supports
0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 0.87g of ethylenediamine tetraacetic acid chelating agent were dissolved in 5mL of deionized water to form impregnating solution A. 1.01g of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form infusion B. Subsequently, the B solution was first impregnated into 5g of a commercial Y molecular sieve (Nanka university catalyst production plant, 350m 2 Per g) on a carrier, drying and then loading the active metal of the impregnation liquid A on the carrierAnd finally drying and roasting the carrier to obtain the Ni-Mo/Y catalyst.
Comparative example 3
3g of gamma-Al is weighed 2 O 3 And deionized water are stirred and mixed uniformly and placed in an oil bath at the constant temperature of 70 ℃. The pH of the solution was adjusted to 1 with dilute nitric acid, 2g of commercial Y molecular sieve was added, and during this period the pH of the system was maintained substantially unchanged by supplementing the appropriate amount of dilute nitric acid, and stirring was continued for 6h. Then ammonia water is adopted to adjust the pH value of the system to 9, standing and ageing are carried out for 3 hours, the catalyst is washed by deionized water, filtered to be neutral by suction, dried and roasted to obtain 40Y-Al 2 O 3 A carrier.
0.87g of Ni (NO) was weighed out 3 ) 2 ·6H 2 O and 1.01g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 5mL deionized water to form an impregnating solution. It was then immersed in 5g 40Meso-USY-Al 2 O 3 Finally, ni-Mo/40Y-Al is obtained by drying and roasting on the carrier 2 O 3 A catalyst.
Experimental example
Evaluation of the reactivity of the catalysts of examples 2 to 7 and comparative examples 1 to 3:
the performance evaluation of the hydrodesulfurization catalytic reaction is carried out on a fixed bed high pressure microreactor.
The catalyst is pressed into tablets and sieved to 40-60 meshes, then 0.2g of the catalyst and 0.6g of quartz sand are weighed, mixed and filled into a reactor, and the hydrodesulfurization reaction performance test is carried out after the pre-vulcanization treatment. The reaction solution is decalin solvent oil containing 2000ppm of 4,6-DMDBT, the reaction solution is pumped into a reactor by a metering pump, and the reaction temperature is 260-320 ℃ and the reaction pressure is 2-5MPa and the space velocity is 2-25h under the pure hydrogen atmosphere with the flow rate of 80-140mL/min -1 The reaction time was 12h. Samples were taken every 1 hour, and the raw material liquid and the reaction liquid were analyzed by Agilent 7890B gas chromatography.
The removal rate of 4,6-DMDBT is calculated as follows:
W in and W is out The mass fraction of 4,6-DMDBT in the raw material and the product is percent respectively.
Table 1, evaluation Table of reactivity of catalysts obtained in different examples and comparative examples
| 4, 6-dimethyl dibenzothiophene removal rate% | |
| Example 2: ni-Mo/Meso-USY | 80 |
| Example 3: ni-Mo/80Meso-USY-Al 2 O 3 | 88 |
| Example 4: ni-Mo/60Meso-USY-Al 2 O 3 | 92 |
| Example 5: ni-Mo/40Meso-USY-Al 2 O 3 | 98 |
| Example 6: ni-Mo/20Meso-USY-Al 2 O 3 | 75 |
| Example 7: co-Mo/40Meso-USY-Al 2 O 3 | 85 |
| Comparative example 1: ni-Mo/Al 2 O 3 | 60 |
| Comparative example 2: ni-Mo/Y | 55 |
| Comparative example 3: ni-Mo/40Y-Al 2 O 3 | 70 |
As can be seen from Table 1, ni-Mo/40Meso-USY-Al 2 O 3 The hydrodesulphurisation activity of the catalyst is higher than that of the other proportions of Meso-USY-Al 2 O 3 A catalyst.
FIG. 1 is a comparison of the reaction properties of 4, 6-dimethyldibenzothiophene of the catalysts of example 2 and comparative example 1, comparative example 2.
FIG. 2 is a comparison of the reaction properties of 4, 6-dimethyldibenzothiophene for the catalysts of example 5 and comparative example 3.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
Claims (10)
1. A hydrodesulfurization catalyst, comprising: an active component, an auxiliary component and a carrier;
the carrier is Meso-USY-Al 2 O 3 A carrier;
the active component is Mo;
the auxiliary component is one or two selected from Ni and Co;
wherein the Meso-USY-Al 2 O 3 The carrier is a multi-stage mesoporous Y molecular sieve and gamma-Al 2 O 3 Is a complex carrier of (a) and (b).
2. Hydrodesulfurization catalyst according to claim 1, characterized in that the active component mass fraction is 9-13wt%.
3. Hydrodesulfurization catalyst according to claim 1, characterized in that the auxiliary agent is present in a mass fraction of 2-5wt%.
4. A method for preparing a hydrodesulfurization catalyst, comprising:
by NaAlO 2 And Na (Na) 2 SiO 3 ·9H 2 O is used for preparing a guiding agent;
mixing the guiding agent with a TPHAC template agent, an aluminum sulfate solution and a KOH solution, and reacting in a polytetrafluoroethylene hydrothermal synthesis kettle to obtain a Y molecular sieve;
combining the Y molecular sieve with (NH) 4 ) 2 SO 4 Sequentially carrying out primary ion exchange, hydrothermal treatment and secondary ion exchange on the solution, and carrying out multi-stage mesoporous Y molecular sieve;
gamma-Al 2 O 3 Preparing Meso-USY-Al with the multilevel mesoporous Y molecular sieve by adopting a sol-gel method 2 O 3 A carrier;
the Meso-USY-Al is modified and impregnated 2 O 3 And loading active components on the carrier to obtain the hydrodesulfurization catalyst.
5. The preparation method according to claim 4, wherein the Meso-USY-Al is prepared by a modified impregnation method 2 O 3 The carrier is loaded with active components to obtain the hydrodesulfurization catalyst which comprises:
dissolving an auxiliary agent and a chelating agent in water to form a first impregnating solution;
dissolving a Mo metal precursor in water to form a second impregnating solution;
subjecting the Meso-USY-Al 2 O 3 And (3) immersing the carrier in the second impregnating solution, drying, immersing in the first impregnating solution, drying again, and roasting to obtain the hydrodesulfurization catalyst.
6. According to claimThe process according to claim 4, wherein the step of preparing the catalyst comprises reacting gamma-Al 2 O 3 Preparing Meso-USY-Al with the multilevel mesoporous Y molecular sieve by adopting a sol-gel method 2 O 3 The carrier comprises:
gamma-Al 2 O 3 Mixing with water, regulating pH to 1-3, adding the multi-stage mesoporous Y molecular sieve, maintaining pH of the system unchanged, stirring for 4-8 hr, regulating pH to 8-10, standing for aging for 2-5 hr, washing, drying, and roasting to obtain the final product 2 O 3 A carrier;
preferably, the said will be gamma-Al 2 O 3 Mixing with water, and adjusting the pH of the solution to 1.
7. The method of claim 5, wherein the chelating agent is selected from the group consisting of: ethylenediamine tetraacetic acid.
8. Use of a hydrodesulfurization catalyst in a 4, 6-dimethyldibenzothiophene hydrodesulfurization reaction, wherein the hydrodesulfurization catalyst is a catalyst according to any one of claims 1 to 3 or a catalyst prepared by a preparation method according to any one of claims 4 to 6.
9. The multi-stage mesoporous molecular sieve is characterized by being prepared by the following method:
by NaAlO 2 And Na (Na) 2 SiO 3 ·9H 2 O is used for preparing a guiding agent;
mixing the guiding agent with a TPHAC template agent, an aluminum sulfate solution and a KOH solution, and reacting in a polytetrafluoroethylene hydrothermal synthesis kettle to obtain a Y molecular sieve;
combining the Y molecular sieve with (NH) 4 ) 2 SO 4 And sequentially carrying out ion exchange, hydrothermal treatment and twice ion exchange on the solution to obtain the multistage mesoporous Y molecular sieve.
10. Use of the multi-stage mesoporous molecular sieve according to claim 9 in the preparation of a 4, 6-dimethyldibenzothiophene hydrodesulfurization catalyst.
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