CN112742404B - Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method - Google Patents
Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method Download PDFInfo
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- CN112742404B CN112742404B CN201911055755.0A CN201911055755A CN112742404B CN 112742404 B CN112742404 B CN 112742404B CN 201911055755 A CN201911055755 A CN 201911055755A CN 112742404 B CN112742404 B CN 112742404B
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- China
- Prior art keywords
- active component
- hydrodesulfurization
- hydrodesulfurization catalyst
- acid
- gasoline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
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- 238000001354 calcination Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 12
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- 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 9
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
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- 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
- B01J35/635—0.5-1.0 ml/g
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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
- C10G45/06—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
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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
- 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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a gasoline selective hydrodesulfurization catalyst, a preparation method and application thereof, and a gasoline selective hydrodesulfurization method. The catalyst comprises a carrier, and an active component A and an active component B which are loaded on the carrier, wherein the active component A is selected from at least one of metal elements of a VIII group, and the active component B is selected from at least one of metal elements of a VIB group; the molybdenum equilibrium adsorption amount of the carrier is MoO 3 3-8% by weight and a specific surface area of 80-200m 2 Per gram, pore volume of 0.5-1cm 3 And/g. When the hydrodesulfurization catalyst provided by the invention is used for the selective hydrodesulfurization reaction of gasoline, the sulfur content in the gasoline can be obviously reduced, and the hydrodesulfurization catalyst has higher hydrodesulfurization rate and lower olefin hydrogenation saturation rate.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a gasoline selective hydrodesulfurization catalyst, a preparation method and application thereof, and a gasoline selective hydrodesulfurization method.
Background
The increasingly stronger environmental awareness and stricter environmental regulations force the oil refining industry to pay more attention to the development of clean fuel production technology, and how to economically and reasonably produce ultralow-sulfur oil products becomes one of the problems which need to be solved in important ways in the oil refining industry at present and in the future in a certain period.
In order to produce clean gasoline, efforts are made at home and abroad to develop a deep hydrodesulfurization catalyst for high-selectivity catalytic cracking gasoline with excellent performance. Hydrogenation catalysts are generally prepared by impregnation, i.e., impregnation of a support with a solution containing the desired active component (e.g., ni, mo, co, W, etc.), followed by drying, calcination, or no calcination.
CN100469440C, CN102909027a discloses that Ni-W-Mo ternary metal hydrogenation catalysts are prepared by introducing organic dispersants or complexing agents (such as ethylene glycol, oxalic acid, citric acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, etc.) into the support during the preparation process. Compared with the catalyst provided by the prior method, the catalyst has better hydrofining performance.
However, when the existing catalyst is used for hydrodesulfurization in catalytically cracked gasoline, olefins in the catalytically cracked gasoline are easily saturated under the hydrodesulfurization reaction conditions, resulting in octane number loss and increased hydrogen consumption. To solve this problem, it is necessary to design and construct an active phase having high hydrodesulfurization activity and selectivity.
Thus, there is a need for a gasoline selective hydrodesulfurization catalyst that has higher hydrodesulfurization activity and selectivity.
Disclosure of Invention
The invention aims to provide a novel gasoline selective hydrodesulfurization catalyst which can obviously reduce the sulfur content in gasoline when being used for the selective hydrodesulfurization reaction of the gasoline, and has higher hydrodesulfurization activity and lower olefin hydrogenation saturation activity.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for selective hydrodesulfurization of gasoline, comprising a carrier and an active component A and an active component B supported on the carrier, wherein the active component A is selected from at least one of group VIII metal elements, and the catalyst comprisesThe active component B is at least one of metal elements of the VIB group; the molybdenum equilibrium adsorption amount of the carrier is MoO 3 3-8% by weight and a specific surface area of 80-200m 2 Per gram, pore volume of 0.5-1cm 3 /g。
Preferably, the molybdenum equilibrium adsorption amount of the carrier is MoO 3 4-6% by weight and a specific surface area of 80-160m 2 Per g, pore volume of 0.5-0.8cm 3 /g。
Preferably, the active component a is Co and/or Ni, more preferably Co; the active component B is Mo and/or W, and is more preferably Mo.
Preferably, the content of the active component A is 0.4 to 4% by weight, more preferably 0.4 to 2.2% by weight, and the content of the active component B is 2 to 8% by weight, more preferably 3.5 to 6% by weight, based on the total amount of the hydrodesulfurization catalyst, on an oxide basis.
The second aspect of the present invention provides a method for preparing the above catalyst, which comprises: the support is impregnated with a solution containing an active component a precursor and an active component B precursor, and then dried and optionally calcined.
Preferably, the solution further comprises a complexing agent selected from at least one of an organic acid and/or an ammonium salt thereof.
Preferably, the molar ratio of complexing agent to active component a precursor, calculated as active component a, is from 0.3 to 2:1.
in a third aspect, the invention provides the use of the catalyst described above in the selective hydrodesulfurization of gasoline.
In a fourth aspect, the present invention provides a process for the selective hydrodesulfurization of gasoline, the process comprising: under the condition of selective hydrodesulfurization of gasoline, gasoline fraction and hydrogen are contacted with the above-mentioned catalyst.
Through the technical scheme, the catalyst carrier with specific properties (with specific molybdenum equilibrium adsorption quantity, specific surface area and pore volume) and the specific active components A and B are matched, so that the activity and selectivity of the catalyst for hydrodesulfurization in the selective hydrodesulfurization reaction of gasoline can be remarkably improved. The preparation method of the catalyst provided by the invention is simple and easy to operate, and the cost is low. In addition, according to the results of the test examples, it can be seen that the product obtained by using the reference agent under the same conditions, using the reaction oil (0.36 wt% of 2-methylthiophene, 20 wt% of n-hexene, and the balance of n-heptane) as the raw material, had a hydrodesulfurization rate of 76% and an olefin hydrogenation saturation rate of 71%; the hydrogenation desulfurization rate of the product obtained by adopting the catalyst provided by the invention can reach 84%, and the olefin hydrogenation saturation rate is only 63%. Compared with the prior art, the catalyst provided by the invention can obviously reduce the sulfur content in gasoline, and has higher hydrodesulfurization rate and lower olefin saturation rate.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a gasoline selective hydrodesulfurization catalyst, which comprises a carrier, and an active component A and an active component B which are loaded on the carrier, wherein the active component A is selected from at least one of metal elements of a VIII group, and the active component B is selected from at least one of metal elements of a VIB group; the molybdenum equilibrium adsorption amount of the carrier is MoO 3 3-8% by weight and a specific surface area of 80-200m 2 Per gram, pore volume of 0.5-1cm 3 /g。
According to the present invention, preferably, the molybdenum equilibrium adsorption amount of the carrier is expressed as MoO 3 4-6% by weight and a specific surface area of 80-160m 2 Per g, pore volume of 0.5-0.8cm 3 And/g. The adoption of the limiting conditions of the carrier which is preferable in the invention is more beneficial to improving the hydrodesulfurization selectivity and the hydrodesulfurization activity of the catalyst.
In the invention, under the condition of no special description, the method for measuring the equilibrium adsorption quantity of molybdenum comprises the following steps: adding into a stainless steel band reaction kettle with stirring and polytetrafluoroethylene lining180g of ammonium heptamolybdate and 7000mL of deionized water are added, 100g of finely ground carrier powder (with granularity smaller than 200 meshes) is added after stirring, dissolving and clarifying, after stirring is continued for 24 hours, all slurry is poured into a Buchner funnel, suction filtration is carried out, deionized water is used for washing 6 times, and the deionized water used for each washing is 7000mL; the filter cake after 6 washes was dried at 120℃for 12 hours and then calcined at 420℃for 4 hours. Measuring MoO of roasted sample by X-ray fluorescence method 3 The percentage content.
In the present invention, the carrier is not particularly limited. Specifically, the support is selected from at least one of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, preferably at least one of alumina, silica and titania. In the examples of the present invention, alumina carriers are used, but the present invention is not limited thereto.
According to the invention, the above-mentioned vectors are commercially available or can be prepared by existing methods.
According to a preferred embodiment of the present invention, the preparation method of the carrier comprises:
(1) Mixing pseudo-boehmite with a solution containing an inorganic aluminum-containing compound to obtain a first slurry;
(2) Adjusting the pH of the slurry to 7-10 to obtain a second slurry;
(3) Aging the second slurry;
(4) And (3) sequentially roasting and hydrothermally treating the ageing product obtained in the step (3).
The inventor of the present invention found that the carrier prepared by the specific method can obtain better hydrodesulfurization effect by matching the active components.
According to a preferred embodiment of the present invention, the pseudo-boehmite is pseudo-boehmite containing no auxiliary agent.
The kind of the inorganic aluminum-containing compound is widely selected, and preferably the inorganic aluminum-containing compound is at least one selected from aluminum sulfate, sodium metaaluminate, aluminum nitrate and aluminum trichloride.
The concentration of the solution containing the inorganic aluminum-containing compound is selected in a wide range in the present invention, for example, al is used per 1000mL of the solution containing the inorganic aluminum-containing compound 2 O 3 The inorganic aluminum-containing compound may be contained in an amount of 1 to 100g, for example, 3 to 65g. The solvent of the solution containing the inorganic aluminum-containing compound may be water.
Preferably, the solution containing the inorganic aluminum-containing compound further contains an organic substance selected from one or more of an organic acid, an organic acid ammonium salt and an organic alcohol.
The organic acid is preferably selected from one or more of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid. The organic acid ammonium salt may be selected from the corresponding ammonium salts of the above organic acids, and the present invention will not be described herein.
The organic alcohol is preferably one or more selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
The invention has a wide selection range of the amount of the organic matters, preferably, the organic matters are mixed with Al 2 O 3 The mass ratio of the inorganic aluminum-containing compound is 0.1-20:1, preferably 0.5 to 10:1.
the invention has a wide selection range of the proportion of the inorganic aluminum-containing compound to the pseudo-boehmite, and preferably uses Al 2 O 3 The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite calculated on a dry basis is 0.1-30:100, preferably 1-20:100, further preferably 5-15:100.
specifically, the mixing of step (1) may be performed under stirring.
According to the invention, in step (2), the pH of the slurry may be adjusted with an acid or a base.
The kind of the acid and the alkali is not particularly limited as long as the pH can be adjusted, the alkali can be hydroxide or a salt which is hydrolyzed in an aqueous medium to make an aqueous solution alkaline, and preferably the hydroxide is one or more selected from urea, ammonia, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from one or more of ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate; the acid may be a protonic acid or an oxide acidic in an aqueous medium, preferably the protonic acid is selected from one or more of nitric acid, sulfuric acid and hydrochloric acid, preferably the oxide is carbon dioxide.
According to a preferred embodiment of the invention, in step (2), the pH of the slurry is adjusted to 8.5-10.
According to the present invention, preferably, the aging conditions include: the temperature is 25-90 ℃ and the time is 0.2-12 hours.
According to one embodiment of the present invention, the preparation method of the carrier further comprises filtering, washing and drying the product obtained by aging in the step (3) to obtain the solid aged product. The specific operations of filtration, washing and drying are not particularly limited in the present invention, and may be performed according to conventional technical means in the art. The drying conditions include, but are not limited to: the temperature is 60-180deg.C, preferably 80-150deg.C; the time is 0.5-24h, preferably 3-12h.
According to a preferred embodiment of the present invention, the conditions for firing include: the temperature is 300-1200 ℃, preferably 400-950 ℃; the time is 0.5-15h, preferably 2-10h.
According to the invention, in particular, the hydrothermal treatment is carried out under closed conditions, for example in a closed reactor. The closed reactor may be any reactor capable of realizing the hydrothermal reaction, for example, a high-pressure reactor, and the reaction may be performed under a static condition or under stirring, and preferably the hydrothermal treatment is performed under stirring.
According to a preferred embodiment of the present invention, the conditions of the hydrothermal treatment include: the mass ratio of water to the solid product obtained by roasting is 1-20:1, preferably 5-10:1, a step of; the temperature is 140-250deg.C, preferably 140-220deg.C; the time is 0.5 to 48 hours, preferably 1 to 24 hours.
Unless otherwise indicated, dry basis in the present invention means: the alumina hydrate was heated to 600 c at a temperature rising rate of 4 c/min in a muffle furnace under an air atmosphere and then kept at 600 c for 4 hours, and the ratio of the weight of the calcined product to the weight of the alumina hydrate before calcination was as high as the percentage, dry basis = weight of the calcined product/(weight of the alumina hydrate before calcination × 100%.
According to one embodiment of the present invention, the preparation method of the carrier further comprises: and sequentially performing first drying, forming and roasting on the product after the hydrothermal treatment. Such an embodiment may result in a carrier suitable for industrial use.
According to the present invention, the condition of the first drying is not particularly limited, and for example, it may be drying at 80 to 150 ℃ for 1 to 24 hours.
According to the invention, the method for preparing the carrier further comprises filtering and washing the product after the hydrothermal treatment before the first drying. The specific operation of the filtration washing is not particularly limited in the present invention, and may be performed according to conventional technical means in the art.
The molding method of the present invention is not particularly limited, and various molding methods conventionally used in the art may be employed, and specifically may include: the product obtained by the first drying is ground and then kneaded with water and optionally an extrusion aid, optionally a binder, and then shaped in a bar extruder. The shape of the molding is not particularly limited in the present invention, and may be any shape applicable to carriers in the art, for example, a sphere or a multiblade shape. The specific operation of the molding is not described here.
According to the present invention, preferably, the conditions of the first firing include: the temperature is 300-1200 ℃, preferably 400-950 ℃; the time is 0.5-15h, preferably 2-10h.
According to the present invention, preferably, the active component a is Co and/or Ni, further preferably Co; the active component B is Mo and/or W, and is more preferably Mo. The inventor of the invention finds that better hydrodesulfurization effect can be obtained by combining Co and Mo with the specific carrier in the research process.
Preferably, the content of the active component A is 0.4 to 4 wt% and the content of the active component B is 2 to 8 wt% in terms of oxides based on the total amount of the hydrodesulfurization catalyst; further preferably, the content of the active component a is 0.4 to 2.2 wt% and the content of the active component B is 3.5 to 6 wt%. Specifically, the content of the active component a is 0.4 wt%, 1 wt%, 2 wt%, 3 wt% and 4 wt%, and any value in the range constituted by any two of these values; the content of the active component B is 2 wt%, 4 wt%, 5 wt%, 6 wt% and 8 wt%, and any value in the range constituted by any two of these values.
The second aspect of the present invention provides a method for preparing the above catalyst, which comprises: the support is impregnated with a solution containing an active component a precursor and an active component B precursor, and then dried and optionally calcined.
According to one embodiment of the invention, the support is impregnated with a solution containing an active component a precursor and an active component B precursor, and then dried.
According to one embodiment of the invention, the support is impregnated with a solution containing an active component a precursor and an active component B precursor, and then dried and calcined.
According to the present invention, the active component a precursor is not particularly limited. Specifically, the active component a precursor may be selected from soluble salts of active component a, which are preferably selected from at least one of nitrate, acetate, basic carbonate and chloride of active component a, more preferably nitrate. Cobalt nitrate hexahydrate is used in the examples of the present invention, but the present invention is not limited thereto.
According to the present invention, the active component B precursor is not particularly limited. Specifically, the active component B precursor may be selected from the group consisting of soluble oxyacid salts of active component B, such as at least one of molybdate, para-molybdate, ammonium dimolybdate, ammonium tetramolybdate, and ammonium heptamolybdate. Ammonium heptamolybdate is used in the examples of the present invention, but the present invention is not limited thereto.
According to a preferred embodiment of the present invention, in the above method for preparing a catalyst, the solution further contains a complexing agent, preferably, the complexing agent is at least one of an organic acid and/or an ammonium salt thereof. Impregnating the support with said solution comprising a complexing agent further facilitates uniform loading of the active component a and of the active component B on said support.
In the present invention, the type of the organic acid and/or the ammonium salt thereof is not particularly limited, and the type selection range of the organic acid and/or the ammonium salt thereof may be as described above, and will not be described in detail herein. Further preferably, the organic acid is citric acid.
Preferably, the molar ratio of complexing agent to active component a precursor, calculated as active component a, is from 0.3 to 2:1.
in the present invention, the impregnation is not particularly limited. In particular, the impregnation is selected from saturated impregnation or excessive impregnation, and when excessive impregnation is used, filtration is required to remove the excess solvent before drying and optionally calcination.
In the present invention, the drying conditions are not particularly limited. Specifically, the drying conditions include: the temperature is 60-180deg.C, preferably 80-150deg.C; the time is 0.5-24h, preferably 3-12h.
In the present invention, the conditions for the calcination are not particularly limited. Specifically, the conditions of the firing include: the temperature is 300-550 ℃, preferably 400-500 ℃; the time is 0.5-15h, preferably 2-10h.
In a third aspect the invention provides the use of the above catalyst in the selective hydrodesulphurisation of petrol. The catalyst provided by the invention is used for the selective hydrodesulfurization of gasoline, has low production cost and has a better hydrodesulfurization effect.
In a fourth aspect, the present invention provides a process for the selective hydrodesulfurization of gasoline, the process comprising: under the condition of selective hydrodesulfurization of gasoline, gasoline fraction and hydrogen are contacted with the above-mentioned catalyst.
The catalyst is preferably presulfided prior to use by methods conventional in the art. In general, the conditions of the prevulcanization may include: presulfiding with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide in the presence of hydrogen at a temperature of 360-400 ℃ for 2-4 hours. The presulfiding can be performed outside the hydrogenation reactor or can be performed in situ within the hydrogenation reactor.
According to the present invention, preferably, the gasoline selective hydrodesulfurization conditions include: the reaction temperature is 200-420 ℃, the pressure is 1-18MPa, and the volume airspeed is 0.3-10h -1 Hydrogen oil volume ratio of 50-5000Nm 3 /m 3 。
Further preferably, the gasoline selective hydrodesulfurization conditions include: the reaction temperature is 250-360 ℃, the pressure is 1-4MPa, and the volume space velocity is 1-6h -1 The volume ratio of hydrogen oil is 200-1000Nm 3 /m 3 。
In the present invention, the gasoline fraction is not particularly limited, and the catalyst provided by the present invention is suitable for selective hydrodesulfurization of various gasoline fractions. Preferably, the gasoline fraction is coker gasoline or catalytically cracked gasoline. Specifically, the sulfur content in the gasoline fraction may be 200-1700 μg/g, and the olefin content 20-40 vol%.
The gasoline selective hydrodesulfurization reaction may be carried out in any reaction apparatus sufficient to contact the gasoline fraction with the catalyst under gasoline selective hydrodesulfurization conditions, for example, the contacting is carried out in a fixed bed reactor, moving bed reactor or ebullated bed reactor, preferably a fixed bed reactor.
Compared with the existing hydrogenation catalyst, the catalyst provided by the invention has low production cost, and has higher hydrodesulfurization activity and higher hydrodesulfurization selectivity.
The present invention will be described in detail by way of specific examples.
In the following examples and comparative examples, the method for measuring the equilibrium adsorption amount of molybdenum was: adding 180g of ammonium heptamolybdate and 7000mL of deionized water into a stainless steel belt reaction kettle with a stirring function and a polytetrafluoroethylene lining, stirring, dissolving and clarifying, adding 100g of finely ground carrier powder (with granularity smaller than 200 meshes), continuously stirring for 24 hours, pouring all slurry into a Buchner funnel, filtering, washing with deionized water for 6 times, and washing with 7000mL of deionized water each time; the filter cake after 6 washes was dried at 120℃for 12 hours and then calcined at 420℃for 4 hours. Measuring MoO of roasted sample by X-ray fluorescence method 3 The percentage content.
The types and contents of the carrier and the active components A and B in the hydrodesulfurization catalyst are shown in Table 1, wherein the contents of the active components A and B in the catalyst are calculated by the feed amount.
Pseudo-boehmite powder (70 wt% on a dry basis) used in the following examples was purchased from catalyst division of petrochemical Co., ltd.
Example 1
In a stirred reaction vessel, an aqueous aluminum sulfate solution (containing Al 2 O 3 Calculated to contain 6 g of Al 2 O 3 ) Is kept at 35 ℃ at a constant temperature of 1000 milliliters; 28 g of glycerol was added, after stirring well, 500 g of pseudo-boehmite powder (70% by weight on a dry basis) was added, after stirring well, concentrated ammonia water (25% by weight) was added, the pH value was adjusted to 9.5, and the mixture was kept for 12 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and keeping the temperature of the filter cake at 600 ℃ for 4 hours in a muffle furnace under the air atmosphere; mixing 300 g with 3000 g deionized water and stirring to obtain slurry; transferring the slurry into an autoclave with a stainless steel band polytetrafluoroethylene lining, wherein the volume of the autoclave is 5 liters, heating the autoclave to 180 ℃ after sealing, and keeping the temperature for 4 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
Grinding the dried product, sieving with 100 mesh sieve, and extruding with extruding machine (manufacturer: general industrial and practical plant of university of south China, model: F-26 (III)) to obtain round with diameter of 1.6 mmIs a clover strip. The wet strips were dried at 120℃for 4 hours and then kept at 600℃for 4 hours in a muffle furnace under an air atmosphere to give alumina carrier S1. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina support S1 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C1.
Example 2
In a stirred reaction vessel, an aqueous aluminum sulfate solution (containing Al 2 O 3 Calculated to contain 63 g of Al 2 O 3 ) Is kept at 90 ℃ at a constant temperature of 1000 milliliters; 69 g of glycerol is added, after stirring uniformly, 500 g of pseudo-boehmite powder (70% by weight on a dry basis) is added, after stirring uniformly, concentrated ammonia water (25% by weight) is added dropwise, the pH value is adjusted to 9.6, and the mixture is kept for 3 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and keeping the temperature of the filter cake at 700 ℃ for 4 hours in a muffle furnace under the air atmosphere; mixing 300 g with 3000 g deionized water and stirring to obtain slurry; transferring the slurry into an autoclave with a stainless steel band polytetrafluoroethylene lining and a stirring volume of 5 liters, heating to 165 ℃ after sealing, and keeping the temperature for 6 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product is ground and sieved by a 100-mesh sieve, and then extruded into clover-shaped strips with the diameter of an external circle of 1.6 mm by a strip extruder (manufacturer: general technical and practical factory of university of south China, model: F-26 (III)). The wet strips were dried at 120℃for 4 hours and then kept at 700℃for 4 hours in a muffle furnace under an air atmosphere to give alumina support S2. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina support S2 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C2.
Example 3
In a stirred reaction vessel, an aqueous aluminum sulfate solution (containing Al 2 O 3 Calculated to contain 63 g of Al 2 O 3 ) Is kept at 90 ℃ at a constant temperature of 1000 milliliters; 500 g of pseudo-boehmite powder (70% by weight on a dry basis) was added, and after stirring well, concentrated aqueous ammonia (25% by weight) was added dropwise, the pH was adjusted to 9.6 and kept for 3 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and keeping the temperature of the filter cake at 700 ℃ for 4 hours in a muffle furnace under the air atmosphere; mixing 300 g with 3000 g deionized water and stirring to obtain slurry; transferring the slurry into an autoclave with a stainless steel band polytetrafluoroethylene lining and a stirring volume of 5 liters, heating to 165 ℃ after sealing, and keeping the temperature for 6 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product is ground and sieved by a 100-mesh sieve, and then extruded into clover-shaped strips with the diameter of an external circle of 1.6 mm by a strip extruder (manufacturer: general technical and practical factory of university of south China, model: F-26 (III)). The wet strips were dried at 120℃for 4 hours and then kept at 600℃for 4 hours in a muffle furnace under an air atmosphere to give alumina supports S3. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S3 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C3.
Example 4
In a stirred reaction vessel, an aqueous aluminum sulfate solution (containing Al 2 O 3 Calculated to contain 35g of Al 2 O 3 ) Is kept at 80 ℃ at a constant temperature of 1000 milliliters; 132 g of glycerol was added, and after stirring well, 500 g of pseudo-boehmite powder (70% by weight on a dry basis) was added, and after stirring well, dropwise adding concentrated ammonia water (25% by weight) was started, and the pH value was adjusted to 9.4 and kept for 3 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and keeping the temperature of 850 ℃ for 4 hours in a muffle furnace under the air atmosphere; mixing 300 g with 3000 g deionized water and stirring to obtain slurry; the slurry was transferred to a stirred stainless steel belt of 5 liter capacity polytetrafluoroHeating the mixture to 175 ℃ after sealing in an autoclave with a lining, and keeping the temperature constant for 5 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product is ground and sieved by a 100-mesh sieve, and then extruded into clover-shaped strips with the diameter of an external circle of 1.6 mm by a strip extruder (manufacturer: general technical and practical factory of university of south China, model: F-26 (III)). The wet strips were dried at 120℃for 4 hours and then kept at 950℃for 4 hours in a muffle furnace under an air atmosphere to give alumina support S4. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina support S4 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C4.
Example 5
In a stirred reaction vessel, an aqueous sodium metaaluminate solution (containing Al 2 O 3 Calculated to contain 80g of Al 2 O 3 ) Is kept at a constant temperature of 85 ℃; 10 g of glycerol, 20 g of glycol, 7 g of polyethylene glycol 200,2 g of citric acid and 1g of ammonium citrate are added, after uniform stirring, 500 g of pseudo-boehmite powder (70 wt% on a dry basis) is added, after uniform stirring, dilute nitric acid (5 wt%) is added dropwise, the pH value is adjusted to 9.3, and the mixture is kept for 3 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and keeping the temperature of 650 ℃ for 6 hours in a muffle furnace under the air atmosphere; mixing 300 g with 2000 g deionized water and stirring to obtain slurry; transferring the slurry into an autoclave with a stainless steel band polytetrafluoroethylene lining, wherein the volume of the autoclave is 5 liters, heating the autoclave to 145 ℃ after sealing, and keeping the temperature constant for 8 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product is ground and sieved by a 100-mesh sieve, and then extruded into clover-shaped strips with the diameter of an external circle of 1.6 mm by a strip extruder (manufacturer: general technical and practical factory of university of south China, model: F-26 (III)). Drying the wet strips at 120deg.C for 4 hr, and keeping the temperature in a muffle furnace at 900deg.C under air atmosphere for 5 hr to obtainAlumina carrier S5. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S5 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C5.
Example 6
Taking 500 g of pseudo-boehmite powder (dry basis 70 wt%) and keeping the temperature of the pseudo-boehmite powder constant at 650 ℃ for 6 hours in a muffle furnace under the air atmosphere; mixing 300 g with 1500 g deionized water and stirring to obtain slurry; transferring the slurry into an autoclave with a stainless steel band polytetrafluoroethylene lining, wherein the volume of the autoclave is 5 liters, heating the autoclave to 175 ℃ after sealing, and keeping the temperature for 5 hours under stirring; after cooling to room temperature and filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product is ground and sieved by a 100-mesh sieve, and then extruded into clover-shaped strips with the diameter of an external circle of 1.6 mm by a strip extruder (manufacturer: general technical and practical factory of university of south China, model: F-26 (III)). The wet strips were dried at 120℃for 4 hours and then kept at 700℃for 5 hours in a muffle furnace under an air atmosphere to give alumina carrier S6. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina support S6 were impregnated with 152mL of an aqueous ammonia solution containing 3.48g of cobalt nitrate hexahydrate, 10.35g of ammonium heptamolybdate and 2.82g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C6.
Example 7
200g of alumina support S1 were impregnated with 152mL of an aqueous ammonia solution containing 10.30g of cobalt nitrate hexahydrate, 15.31g of ammonium heptamolybdate and 8.35g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C7.
Example 8
200g of alumina support S1 were impregnated with 152mL of an aqueous ammonia solution containing 5.70g of cobalt nitrate hexahydrate, 11.30g of ammonium heptamolybdate and 4.62g of ammonium citrate; the impregnation time was 2h, after which the impregnated product was dried at 120℃for 4h and calcined at 450℃for 3h to give catalyst C8.
Comparative example 1
500 g of pseudo-boehmite powder (dry basis: 70% by weight) was weighed and extruded into clover-shaped bars with an circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general technical practice of the university of south China, model number F-26 (III)). The wet strips were dried at 120℃for 4 hours and then kept at 600℃for 4 hours in a muffle furnace under an air atmosphere to give alumina carrier DT-1. Through N 2 The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
A catalyst was prepared in the same manner as in example 1 except that the alumina carrier S1 was replaced with an alumina carrier DT-1 of equal mass to obtain a catalyst D1.
TABLE 1
Note that: in table 1, the Co content and Mo content are both calculated as oxides.
Test case
Crushing the catalyst into particles with 40-60 meshes, and loading 1g of crushed catalyst into a reactor constant temperature area of a hydrogenation test device of the micro reactor. The vulcanized oil adopts 5w percent of carbon disulfide/cyclohexane, the flow is 0.2ml/min, and the hydrogen flow rate is 180ml/min. And vulcanizing at a constant temperature of 360 ℃ for 3 hours. After completion of vulcanization, when the temperature was lowered to 263 ℃, the vulcanized oil was changed to a model reaction oil (0.36% by weight of 2-methylthiophene, 20% by weight of n-hexene, the balance being n-heptane). The selective hydrodesulfurization reaction was evaluated at a reaction pressure of 1.6MPa, a reaction temperature of 263℃and a feed rate of 0.2ml/min, and a hydrogen flow rate of 180ml/min. After steady state was reached, product composition analysis was performed on-line using an Agilent model 7890 gas chromatograph. The hydrodesulfurization (HDS%) and olefin hydrogenation saturation (HYD%) of the catalyst are calculated according to the formulas (1) to (2), respectively.
HDS％＝[(w1-w2)/w1]×100％ (1)
HYD％＝[(w3-w4)/w3]×100％ (2)
In the formulas (1) - (2), w1 and w2 respectively represent the mass fraction,%;
w3 and w4 represent the mass fraction,%, of 1-hexene in the reactants and products, respectively. The specific evaluation results are shown in Table 2.
TABLE 2
As can be seen from the results in Table 2, when the hydrodesulfurization catalyst of the invention is used for selective hydrodesulfurization, the sulfur content in the oil product can be significantly reduced, the olefin hydrogenation saturation rate is low, and the hydrodesulfurization activity and selectivity are relatively high.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (27)
1. The catalyst comprises a carrier, and an active component A and an active component B which are supported on the carrier, wherein the active component A is selected from at least one of metal elements in a VIII group, and the active component B is selected from at least one of metal elements in a VIB group; the molybdenum equilibrium adsorption amount of the carrier is MoO 3 3-8% by weight and a specific surface area of 80-160m 2 Per gram, pore volume of 0.5-1cm 3 /g；
The content of the active component A is 0.4 to 4 weight percent and the content of the active component B is 2 to 8 weight percent based on the total amount of the hydrodesulfurization catalyst and calculated as oxide.
2. The hydrodesulfurization catalyst according to claim 1, wherein the molybdenum equilibrium adsorption amount of the support is expressed as MoO 3 4-6%, and pore volume of 0.5-0.8cm 3 /g。
3. The hydrodesulfurization catalyst according to claim 1, wherein the support is at least one selected from the group consisting of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
4. The hydrodesulfurization catalyst according to claim 1, wherein the carrier is prepared by a process comprising:
(1) Mixing pseudo-boehmite with a solution containing an inorganic aluminum-containing compound to obtain a first slurry;
(2) Adjusting the pH of the slurry to 7-10 to obtain a second slurry;
(3) Aging the second slurry;
(4) And (3) sequentially roasting and hydrothermally treating the solid ageing product obtained in the step (3).
5. The hydrodesulfurization catalyst according to claim 4, wherein step (2) adjusts the pH of the slurry to 8.5 to 10 to obtain a second slurry;
and/or, the aging conditions of step (3) include: the temperature is 25-90 ℃ and the time is 0.2-12 hours.
6. The hydrodesulfurization catalyst according to claim 4, wherein the conditions of the calcination include: the temperature is 300-1200 ℃; the time is 0.5-15h;
and/or, the conditions of the hydrothermal treatment include: the mass ratio of water to the solid product obtained by roasting is 1-20:1, a step of; the temperature is 140-250 ℃; the time is 0.5-48 hours.
7. The hydrodesulfurization catalyst according to claim 6, wherein the conditions of the calcination include: the temperature is 400-950 ℃; the time is 2-10h;
and/or, the conditions of the hydrothermal treatment include: the mass ratio of water to the solid product obtained by roasting is 5-10:1, a step of; the temperature is 140-220 ℃; the time is 1-24 hours.
8. The hydrodesulfurization catalyst according to claim 4, wherein the solution containing an inorganic aluminum-containing compound in step (1) further contains an organic substance selected from one or more of an organic acid, an organic acid ammonium salt and an organic alcohol.
9. The hydrodesulfurization catalyst according to claim 8, wherein the organic compound is mixed with a catalyst comprising Al 2 O 3 The mass ratio of the inorganic aluminum-containing compound is 0.1-20:1.
10. the hydrodesulfurization catalyst according to claim 9, wherein the organic compound is mixed with a catalyst comprising Al 2 O 3 The mass ratio of the inorganic aluminum-containing compound is 0.5-10:1.
11. the hydrodesulfurization catalyst according to claim 4, wherein Al is used as 2 O 3 The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite calculated on a dry basis is 0.1-30:100.
12. the hydrodesulfurization catalyst according to claim 11, wherein Al is used as 2 O 3 The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite calculated on a dry basis is 1-20:100.
13. according to the weightsThe hydrodesulfurization catalyst of claim 12, wherein Al is used as 2 O 3 The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite calculated on a dry basis is 5-15:100.
14. the hydrodesulfurization catalyst according to claim 4, wherein the inorganic aluminum-containing compound is selected from at least one of aluminum sulfate, sodium metaaluminate, aluminum nitrate, and aluminum trichloride.
15. The hydrodesulfurization catalyst according to any one of claims 1 to 14, wherein the active component a is Co and/or Ni; the active component B is Mo and/or W.
16. The hydrodesulfurization catalyst of claim 15, wherein the active component a is Co; the active component B is Mo.
17. The hydrodesulfurization catalyst according to claim 1, wherein the active component a is contained in an amount of 0.4 to 2.2% by weight and the active component B is contained in an amount of 3.5 to 6% by weight on an oxide basis based on the total amount of the hydrodesulfurization catalyst.
18. A process for preparing a gasoline selective hydrodesulfurization catalyst as claimed in any one of claims 1 to 17, which process comprises:
the support is impregnated with a solution containing an active component a precursor and an active component B precursor, and then dried and optionally calcined.
19. The method according to claim 18, wherein the solution further contains a complexing agent selected from at least one of an organic acid and/or an ammonium salt thereof.
20. The process according to claim 19, wherein the organic acid is at least one selected from trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid.
21. The method of claim 19, wherein the molar ratio of complexing agent to active component a precursor is from 0.3 to 2:1.
22. the method of manufacturing according to claim 18, wherein the drying conditions include: the temperature is 60-180 ℃; the time is 0.5-24h;
and/or, the roasting conditions include: the temperature is 300-550 ℃; the time is 0.5-15h.
23. The method of manufacturing according to claim 22, wherein the drying conditions include: the temperature is 80-150 ℃; the time is 3-12h;
and/or, the roasting conditions include: the temperature is 400-500 ℃; the time is 2-10h.
24. Use of the catalyst of any one of claims 1-17 in the selective hydrodesulfurization of gasoline.
25. A process for the selective hydrodesulfurization of gasoline, the process comprising: contacting a gasoline fraction, hydrogen, and the gasoline selective hydrodesulfurization catalyst of any one of claims 1-17 under gasoline selective hydrodesulfurization conditions.
26. The method of claim 25, wherein the gasoline selective hydrodesulfurization conditions comprise: the reaction temperature is 200-420 ℃, the pressure is 1-18MPa, and the volume airspeed is 0.3-10h -1 Hydrogen oil volume ratio of 50-5000Nm 3 /m 3 。
27. The method of claim 25, wherein the gasoline selective hydrodesulfurization conditions comprise: the reaction temperature is 250-360 ℃, the pressure is 1-4MPa, and the volume space velocity is 1-6h -1 Hydrogen oil bodyThe product ratio is 200-1000Nm 3 /m 3 。
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| JP2005220301A (en) * | 2004-02-09 | 2005-08-18 | Catalysts & Chem Ind Co Ltd | Hydrodesulfurization method of gas oil |
| CN103468303A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for selective hydrodesulfurization of gasoline |
| CN106140316A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof |
| CN106362757A (en) * | 2015-07-21 | 2017-02-01 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and applications thereof |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
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| JP2005220301A (en) * | 2004-02-09 | 2005-08-18 | Catalysts & Chem Ind Co Ltd | Hydrodesulfurization method of gas oil |
| CN103468303A (en) * | 2012-06-07 | 2013-12-25 | 中国石油化工股份有限公司 | Method for selective hydrodesulfurization of gasoline |
| CN106140316A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof |
| CN106362757A (en) * | 2015-07-21 | 2017-02-01 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and applications thereof |
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