CN112742404A - 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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- 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
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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
- B01J35/61—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)
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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 VIII group metal elements, and the active component B is selected from at least one of VIB group metal elements; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 3-8%, the specific surface area is 80-200m2Per g, pore volume of 0.5-1cm3(ii) in terms of/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, and particularly relates to a gasoline selective hydrodesulfurization catalyst, a preparation method and application thereof, and a gasoline selective hydrodesulfurization method.
Background
The increasing awareness of environmental protection and stricter regulations of environmental protection force the oil refining world to pay more attention to the development of clean fuel production technology, and how to economically and reasonably produce ultra-low sulfur oil products becomes one of the problems to be solved in the oil refining world at present and in a certain period in the future.
In order to produce clean gasoline, the deep hydrodesulfurization catalyst of high-selectivity catalytic cracking gasoline with excellent performance is researched at home and abroad. Hydrogenation catalysts are typically prepared by impregnation, i.e., by impregnating 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 disclose that Ni-W-Mo ternary metal hydrogenation catalysts are prepared by introducing organic dispersing agents or complexing agents (such as ethylene glycol, oxalic acid, citric acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, etc.) into the carrier during the preparation process. Compared with the catalyst provided by the existing method, the obtained catalyst has better hydrofining performance.
However, when the existing catalyst is used for hydrodesulfurization in catalytic gasoline, olefins in the catalytic gasoline are easily saturated under hydrodesulfurization reaction conditions, resulting in octane number loss and hydrogen consumption increase. To solve this problem, it is necessary to design and construct an active phase having high hydrodesulfurization activity and selectivity.
Therefore, a gasoline selective hydrodesulfurization catalyst with higher hydrodesulfurization activity and selectivity is needed.
Disclosure of Invention
The invention aims to provide a novel gasoline selective hydrodesulfurization catalyst which can obviously reduce the sulfur content in gasoline and has higher hydrodesulfurization activity and lower olefin hydrogenation saturation activity when being used in the gasoline selective hydrodesulfurization reaction.
In order to achieve the above object, a first aspect of the present invention provides a gasoline selective hydrodesulfurization catalyst, which comprises 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 active component B is selected from at least one of group VIB metal elements; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 3-8%, the specific surface area is 80-200m2Per g, pore volume of 0.5-1cm3/g。
Preferably, the molybdenum equilibrium adsorption amount of the carrier is MoO3Calculated as 4-6%, the specific surface area is 80-160m2Per g, pore volume of 0.5-0.8cm3/g。
Preferably, the active component a is Co and/or Ni, more preferably Co; the active component B is Mo and/or W, and Mo is further preferable.
Preferably, the content of the active component a is 0.4 to 4 wt%, more preferably 0.4 to 2.2 wt%, and the content of the active component B is 2 to 8 wt%, more preferably 3.5 to 6 wt%, in terms of oxide, based on the total amount of the hydrodesulfurization catalyst.
In a second aspect, the present invention provides a method for preparing the above catalyst, which comprises: the carrier is impregnated with a solution containing a precursor of active component a and a precursor of active component B, followed by drying and optionally calcination.
Preferably, the solution further contains a complexing agent, and the complexing agent is selected from at least one of organic acid and/or ammonium salt thereof.
Preferably, the mol ratio of the complexing agent to the active component A precursor calculated by the active component A is 0.3-2: 1.
the third aspect of the invention provides an application of the catalyst in selective hydrodesulfurization of gasoline.
In a fourth aspect, the present invention provides a method for selective hydrodesulfurization of gasoline, the method comprising: under the condition of selective hydrodesulfurization of gasoline, gasoline fraction and hydrogen are contacted with the catalyst.
Through the technical scheme, the activity and the selectivity of the catalyst for hydrodesulfurization in gasoline selective hydrodesulfurization reaction can be remarkably improved by matching the catalyst carrier with specific properties (with specific molybdenum equilibrium adsorption capacity, specific surface area and pore volume) with specific active components A and B. The preparation method of the catalyst provided by the invention is simple and easy to operate, and has low cost. In addition, according to the results of the test examples, the hydrodesulfurization rate of the product obtained by 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 and using the reference agent under the same conditions is 76%, and the olefin hydrogenation saturation rate is 71%; the hydrodesulfurization rate of the product obtained by using 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a gasoline selective hydrodesulfurization catalyst in a first aspect, which comprises a carrier and an active component A and an active component which are loaded on the carrierB, the active component A is selected from at least one of VIII group metal elements, and the active component B is selected from at least one of VIB group metal elements; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 3-8%, the specific surface area is 80-200m2Per g, pore volume of 0.5-1cm3/g。
According to the invention, the molybdenum equilibrium adsorption quantity of the carrier is MoO3Calculated as 4-6%, the specific surface area is 80-160m2Per g, pore volume of 0.5-0.8cm3(ii) in terms of/g. The adoption of the preferable limited conditions of the carrier is more beneficial to improving the hydrodesulfurization selectivity and the hydrodesulfurization activity of the catalyst.
In the present invention, unless otherwise specified, the method for measuring the equilibrium adsorption amount of molybdenum is as follows: adding 180g of ammonium heptamolybdate and 7000mL of deionized water into a stainless steel strip reaction kettle with a stirring and polytetrafluoroethylene lining, stirring, dissolving and clarifying, adding 100g of ground carrier powder (the granularity is less than 200 meshes), continuously stirring for 24h, pouring all the slurry into a Buchner funnel, and carrying out suction filtration and washing with deionized water for 6 times, wherein the deionized water used in each washing is 7000 mL; the filter cake after 6 times of washing is dried at 120 ℃ for 12h and then roasted at 420 ℃ for 4 h. Determining MoO of the roasted sample by adopting an X fluorescence method3The percentage content is as follows.
In the present invention, the carrier is not particularly limited. Specifically, the carrier 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, and is preferably at least one of alumina, silica and titania. In the examples of the present invention, an alumina carrier is used, but the present invention is not limited thereto.
According to the present invention, the above-mentioned carrier can be obtained commercially or can be prepared by a conventional method.
According to a preferred embodiment of the present invention, the method for preparing 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 (4) sequentially roasting and carrying out hydrothermal treatment on the aged product obtained in the step (3).
The inventors of the present invention have found that the carrier prepared by the specific method can achieve a better hydrodesulfurization effect by combining the active component.
According to a preferred embodiment of the present invention, the pseudoboehmite is a pseudoboehmite containing no assistant.
The invention has wide selection of the kind of the inorganic aluminum-containing compound, and preferably, the inorganic aluminum-containing compound is selected from at least one of 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, for example, every 1000mL of the solution containing the inorganic aluminum-containing compound is mixed with Al2O3The inorganic aluminium-containing compound may be present in an amount of 1 to 100g, for example 3 to 65 g. 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, and the organic substance is one or more selected from organic acids, organic acid ammonium salts and organic alcohols.
The organic acid is preferably selected from one or more of trans-1, 2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid. The organic acid ammonium salt can be selected from the corresponding organic acid ammonium salts, and the invention is not described herein again.
The organic alcohol is preferably selected from one or more of glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
The invention has wide selection range of the dosage of the organic matter, and preferably, the organic matter and Al are used2O3The mass ratio of the inorganic aluminum-containing compound is 0.1-20: 1, preferably 0.5 to 10: 1.
the invention has wide selection range of the dosage ratio of the inorganic aluminum-containing compound to the pseudo-boehmite, and preferably, Al is used2O3The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite in a dry basis is 0.1-30: 100, preferably 1 to 20: 100, more preferably 5 to 15: 100.
specifically, the mixing of step (1) may be performed under stirring conditions.
According to the present invention, in the step (2), the pH of the slurry may be adjusted with an acid or a base.
The types of the acid and the alkali are not particularly limited, as long as the function of adjusting the pH is achieved, the alkali can be hydroxide or salt which is hydrolyzed in an aqueous medium to make an aqueous solution alkaline, and the hydroxide is preferably one or more selected from urea, ammonia water, 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 can be protonic acid or oxide which is acidic in an aqueous medium, preferably the protonic acid is one or more selected from nitric acid, sulfuric acid and hydrochloric acid, and preferably the oxide is carbon dioxide.
According to a preferred embodiment of the present invention, in the step (2), the pH of the slurry is adjusted to 8.5 to 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 a specific embodiment of the present invention, the preparation method of the carrier further comprises filtering, washing and drying the aged product of step (3) to obtain the solid aged product. The specific operations of filtering, washing and drying are not particularly limited in the present invention, and can be performed according to the conventional technical means in the art. The drying conditions include, but are not limited to: the temperature is 60-180 ℃, preferably 80-150 ℃; the time is 0.5-24h, preferably 3-12 h.
According to a preferred embodiment of the present invention, the conditions of the calcination include: the temperature is 300-1200 ℃, and preferably 400-950 ℃; the time is 0.5-15h, preferably 2-10 h.
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 carrying out the hydrothermal reaction, for example, an autoclave, and the reaction may be carried out under a static condition or under a stirred condition, and preferably the hydrothermal treatment is carried out under a stirred condition.
According to a preferred embodiment of the present invention, the conditions of the hydrothermal treatment include: the mass ratio of water to solid products obtained by roasting is 1-20: 1, preferably 5 to 10: 1; the temperature is 140 ℃ to 250 ℃, preferably 140 ℃ to 220 ℃; the time is 0.5 to 48 hours, preferably 1 to 24 hours.
The dry basis in the present invention means, unless otherwise specified: the alumina hydrate was raised to 600 ℃ in a muffle furnace under air atmosphere at a rate of 4 ℃/min and then kept at 600 ℃ for 4 hours, the percentage of the weight of the product after calcination to the weight of the alumina hydrate before calcination being dry-basis ÷ the weight of the product after calcination ÷ the weight of the alumina hydrate before calcination × 100%.
According to a specific embodiment of the present invention, the method for preparing the carrier further comprises: and sequentially carrying out first drying, forming and roasting on the product after the hydrothermal treatment. This embodiment gives a carrier suitable for industrial use.
According to the present invention, the conditions of the first drying are not particularly limited, and for example, the drying may be performed at 80 to 150 ℃ for 1 to 24 hours.
According to the present invention, specifically, the preparation method of the carrier further comprises subjecting the product after the hydrothermal treatment to filtration washing before the first drying. The specific operation of the filtration washing in the present invention is not particularly limited, and may be carried out according to a conventional technique 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, the molding method may include: grinding the product obtained by the first drying, kneading the ground product with water, an optional extrusion aid and an optional binder, and forming the product in a strip extruder. The shape of the molded article is not particularly limited in the present invention, and may be any shape applicable to carriers in the art, for example, a spherical shape or a multi-lobal shape. The specific operation of the molding is not described herein again.
According to the present invention, preferably, the conditions of the first firing include: the temperature is 300-1200 ℃, and preferably 400-950 ℃; the time is 0.5-15h, preferably 2-10 h.
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 Mo is further preferable. In the research process, the inventor of the invention finds that better hydrodesulfurization effect can be obtained by matching Co and Mo with the specific carrier of the invention.
Preferably, the content of the active component A is 0.4-4 wt% and the content of the active component B is 2-8 wt% in terms of oxide based on the total amount of the hydrodesulfurization catalyst; further preferably, the content of the active component A is 0.4-2.2 wt%, and the content of the active component B is 3.5-6 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 of any two of these values; the active ingredient B is present in an amount of 2 wt%, 4 wt%, 5 wt%, 6 wt%, and 8 wt%, and any value within the range of any two of these values.
In a second aspect, the present invention provides a method for preparing the above catalyst, which comprises: the carrier is impregnated with a solution containing a precursor of active component a and a precursor of active component B, followed by drying and optionally calcination.
According to one embodiment of the invention, the support is impregnated with a solution containing a precursor of active component a and a precursor of active component B, and then dried.
According to one embodiment of the invention, the support is impregnated with a solution containing a precursor of active component a and a precursor of active component B, followed by drying and calcination.
According to the present invention, the precursor of the active component a is not particularly limited. Specifically, the active component a precursor may be selected from soluble salts of the active component a, and the soluble salt of the active component a is preferably selected from at least one of nitrate, acetate, basic carbonate and chloride of the active component a, and more preferably is 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 precursor of the active component B is not particularly limited. Specifically, the active component B precursor may be selected from the group consisting of oxyacid salts of soluble active component B of active component B, such as at least one of molybdate, paramolybdate, 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, and preferably, the complexing agent is at least one selected from organic acids and/or ammonium salts thereof. The carrier is impregnated with the solution containing the complexing agent, which is more favorable for uniformly loading the active component A and the active component B on the carrier.
In the present invention, there is no particular limitation on the kind of the organic acid and/or the ammonium salt thereof, and the selection range of the kind of the organic acid and/or the ammonium salt thereof may be as described above, and will not be described herein again. Further preferably, the organic acid is citric acid.
Preferably, the mol ratio of the complexing agent to the active component A precursor calculated by the active component A is 0.3-2: 1.
in the present invention, the impregnation is not particularly limited. In particular, the impregnation is selected from saturation impregnation or excess impregnation, when excess impregnation is employed, filtration is required to remove excess solvent before drying and optionally calcining.
In the present invention, the drying conditions are not particularly limited. Specifically, the drying conditions include: the temperature is 60-180 ℃, preferably 80-150 ℃; the time is 0.5-24h, preferably 3-12 h.
In the present invention, the conditions for the calcination are not particularly limited. Specifically, the roasting conditions include: the temperature is 300-550 ℃, and preferably 400-500 ℃; the time is 0.5-15h, preferably 2-10 h.
In a third aspect, the invention provides the use of the above catalyst in the selective hydrodesulfurization of gasoline. The catalyst provided by the invention is used for selective hydrodesulfurization of gasoline, and has low production cost and better hydrodesulfurization effect.
In a fourth aspect, the present invention provides a method for selective hydrodesulfurization of gasoline, the method comprising: under the condition of selective hydrodesulfurization of gasoline, gasoline fraction and hydrogen are contacted with the catalyst.
The catalyst is preferably presulfided prior to use using methods conventional in the art. In general, the conditions of the prevulcanisation 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-. The pre-vulcanization can be carried out outside the hydrogenation reactor or can be carried out in situ in the hydrogenation reactor.
According to the present invention, preferably, the gasoline selective hydrodesulfurization conditions comprise: the reaction temperature is 200 ℃ and 420 ℃, the pressure is 1-18MPa, and the volume space velocity is 0.3-10h-1The volume ratio of hydrogen to oil is 50-5000Nm3/m3。
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-1The volume ratio of hydrogen to oil is 200-1000Nm3/m3。
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. mu.g/g, and the olefin content may be 20-40 vol%.
The gasoline selective hydrodesulfurization reaction can be carried out in any reaction apparatus sufficient to effect contact reaction of the gasoline fraction with the catalyst under gasoline selective hydrodesulfurization conditions, for example, the contact is carried out in a fixed bed reactor, a moving bed reactor, or an ebullating bed reactor, preferably a fixed bed reactor.
Compared with the existing hydrogenation catalyst, the catalyst provided by the invention has the advantages of low production cost, higher hydrodesulfurization activity and higher hydrodesulfurization selectivity.
The present invention will be described in detail below by way of specific examples.
In the following examples and comparative examples, the equilibrium adsorption amount of molybdenum was measured by: adding 180g of ammonium heptamolybdate and 7000mL of deionized water into a stainless steel strip reaction kettle with a stirring and polytetrafluoroethylene lining, stirring, dissolving and clarifying, adding 100g of ground carrier powder (the granularity is less than 200 meshes), continuously stirring for 24h, pouring all the slurry into a Buchner funnel, and carrying out suction filtration and washing with deionized water for 6 times, wherein the deionized water used in each washing is 7000 mL; the filter cake after 6 times of washing is dried at 120 ℃ for 12h and then roasted at 420 ℃ for 4 h. Determining MoO of the roasted sample by adopting an X fluorescence method3The percentage content is as follows.
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 feeding amount.
Pseudo-boehmite powder (70 wt% on a dry basis) used in the following examples was obtained from catalyst division, petrochemicals, Inc., China.
Example 1
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, contains 6 g of Al2O3) 1000 milliRaising the temperature and keeping the temperature at 35 ℃; adding 28 g of glycerol, stirring uniformly, adding 500 g of pseudo-boehmite powder (dry basis is 70 wt%), stirring uniformly, adding concentrated ammonia water (25 wt%), adjusting the pH value to 9.5, and keeping for 12 hours. Filtering and washing, drying the obtained filter cake for 8 hours at 120 ℃, and then keeping the temperature of the filter cake in a muffle furnace for 4 hours at 600 ℃ in the air atmosphere; mixing 300 g and 3000 g of deionized water, and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 180 ℃, 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.
The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S1. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S1 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C1.
Example 2
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, 63 g of Al2O3) 1000ml of (1), and keeping the temperature at 90 ℃; 69 g of glycerol is added, after uniform stirring, 500 g of pseudo-boehmite powder (dry basis is 70 wt%) is added, after uniform stirring, concentrated ammonia water (25 wt%) 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 for 8 hours at 120 ℃, and keeping the temperature of the filter cake in a muffle furnace at 700 ℃ for 4 hours in an air atmosphere; mixing 300 g and 3000 g of deionized water, and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 165 ℃, and keeping the temperature for 6 hours under stirring; then, the temperature is reduced to room temperatureAfter filtration, the filter cake was dried at 120 ℃ for 8 hours.
The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 700 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S2. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S2 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C2.
Example 3
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, 63 g of Al2O3) 1000ml of (1), and keeping the temperature at 90 ℃; adding 500 g of pseudo-boehmite powder (dry basis is 70 wt%), stirring uniformly, then beginning to drop concentrated ammonia (25 wt%), adjusting pH value to 9.6, and keeping for 3 hours. Filtering and washing, drying the obtained filter cake for 8 hours at 120 ℃, and keeping the temperature of the filter cake in a muffle furnace at 700 ℃ for 4 hours in an air atmosphere; mixing 300 g and 3000 g of deionized water, and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 165 ℃, 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 was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S3. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S3 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C3.
Example 4
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Calculated, 35g Al2O3) 1000ml of (1), and keeping the temperature at 80 ℃; adding 132 g of glycerol, stirring uniformly, adding 500 g of pseudo-boehmite powder (dry basis is 70 wt%), stirring uniformly, then beginning to dropwise add concentrated ammonia water (25 wt%), adjusting the pH value to 9.4, and keeping for 3 hours. Filtering and washing, drying the obtained filter cake for 8 hours at 120 ℃, and then keeping the temperature of the filter cake constant for 4 hours at 850 ℃ in a muffle furnace under the air atmosphere; mixing 300 g and 3000 g of deionized water, and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 175 ℃, 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 was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 950 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S4. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S4 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C4.
Example 5
Preparing sodium metaaluminate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Calculated, containing 80g Al2O3) 1000ml of (1), and keeping the temperature at 85 ℃; adding 10 g of glycerol, 20 g of ethylene glycol, 7 g of polyethylene glycol 200, 2g of citric acid and 1g of ammonium citrate, stirring uniformly, and then adding 500 g of pseudo-boehmite powder (70% by weight of dry basis)) After stirring uniformly, dilute nitric acid (5 wt%) was added dropwise to adjust the pH to 9.3 and the mixture was kept for 3 hours. Filtering and washing, drying the obtained filter cake at 120 ℃ for 8 hours, and then keeping the temperature of 650 ℃ in a muffle furnace for 6 hours in the air atmosphere; mixing 300 g and 2000 g of deionized water and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 145 ℃, and keeping the temperature 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 was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 900 ℃ in a muffle furnace under an air atmosphere for 5 hours to obtain an alumina support S5. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S5 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C5.
Example 6
500 g of pseudo-boehmite powder (dry basis is 70 weight percent) is taken and is kept at the constant temperature of 650 ℃ in a muffle furnace for 6 hours under the air atmosphere; mixing 300 g of deionized water and 1500 g of deionized water and stirring to obtain slurry; transferring the slurry into a stainless steel autoclave with a 5L capacity and a polytetrafluoroethylene lining, sealing, heating to 175 ℃, 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 was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 700 ℃ in a muffle furnace under an air atmosphere for 5 hours to obtain an alumina support S6. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
200g of alumina carrier S6 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C6.
Example 7
200g of alumina carrier S1 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C7.
Example 8
200g of the alumina carrier S1 was 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 is 2h, then the impregnated product is dried for 4h at 120 ℃ and roasted for 3h at 450 ℃ to obtain the catalyst C8.
Comparative example 1
500 g of pseudo-boehmite powder (70 wt% on a dry basis) was weighed and extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a strip extruder (manufacturer: general plant of science and technology industries of southern China university, type: F-26 (III)). And drying the wet strip at 120 ℃ for 4 hours, and keeping the temperature of the wet strip in a muffle furnace at 600 ℃ for 4 hours in an air atmosphere to obtain the alumina carrier DT-1. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
A catalyst was prepared by following the procedure of example 1, except that the alumina support S1 was replaced with an equal mass of alumina support DT-1, to obtain catalyst D1.
TABLE 1
Note: in table 1, the Co content and Mo content are both in terms of oxides.
Test example
The catalyst is crushed into particles of 40-60 meshes, and 1g of the crushed catalyst is loaded into a reactor constant-temperature area of a hydrogenation test device of a microreactor. The sulfurated oil adopts 5 w% carbon disulfide/cyclohexane, the flow rate is 0.2ml/min, and the hydrogen flow rate is 180 ml/min. Vulcanizing at constant temperature of 360 ℃ for 3 hours. After the vulcanization is finished, when the temperature is reduced to 263 ℃, the vulcanized oil is switched to model reaction oil (0.36 wt% of 2-methylthiophene, 20 wt% of n-hexene, and the balance of n-heptane). And carrying out selective hydrodesulfurization reaction evaluation, wherein the reaction pressure is 1.6MPa, the reaction temperature is 263 ℃, the feeding rate is 0.2ml/min, and the hydrogen flow rate is 180 ml/min. After reaching the steady state, the product composition was analyzed on-line using an Agilent model 7890 gas chromatograph. The hydrodesulfurization rate (HDS%) and the olefin hydrogenation saturation rate (HYD%) of the catalyst were calculated in accordance with the formulas (1) to (2), respectively.
HDS％＝[(w1-w2)/w1]×100％ (1)
HYD％＝[(w3-w4)/w3]×100％ (2)
In the formulae (1) to (2), w1 and w2 represent the mass fraction,%, of 2-methylthiophene in the reactant and the product, respectively;
w3 and w4 represent the mass fraction of 1-hexene in the reactant and product, respectively,%. The specific evaluation results are shown in Table 2.
TABLE 2
The results in table 2 show that the hydrodesulfurization catalyst of the present invention can significantly reduce the sulfur content in the oil product when used in the selective hydrodesulfurization reaction, and the olefin hydrogenation saturation ratio is low, and the hydrodesulfurization catalyst has high hydrodesulfurization activity and selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A gasoline selective hydrodesulfurization 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 VIII group metal elements, and the active component B is selected from at least one of VIB group metal elements; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 3-8%, the specific surface area is 80-200m2Per g, pore volume of 0.5-1cm3/g。
2. The hydrodesulfurization catalyst of claim 1 wherein the equilibrium adsorption amount of molybdenum on the support is MoO3Calculated as 4-6%, the specific surface area is 80-160m2Per g, pore volume of 0.5-0.8cm3/g。
3. The hydrodesulfurization catalyst of claim 1 wherein 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, the preparation method of the carrier comprises the following steps:
(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, preferably 8.5-10, to obtain a second slurry;
(3) aging the second slurry, preferably under conditions comprising: the temperature is 25-90 ℃ and the time is 0.2-12 hours;
(4) sequentially roasting and carrying out hydrothermal treatment on the solid aging product obtained in the step (3);
preferably, the conditions of the calcination include: the temperature is 300-1200 ℃, and preferably 400-950 ℃; the time is 0.5 to 15 hours, preferably 2 to 10 hours;
preferably, the conditions of the hydrothermal treatment include: the mass ratio of water to solid products obtained by roasting is 1-20: 1, preferably 5 to 10: 1; the temperature is 140 ℃ to 250 ℃, preferably 140 ℃ to 220 ℃; the time is 0.5 to 48 hours, preferably 1 to 24 hours.
4. The hydrodesulfurization catalyst of claim 3 wherein the solution containing the inorganic aluminum-containing compound of step (1) further contains an organic material selected from one or more of an organic acid, an ammonium salt of an organic acid and an organic alcohol; preferably, the organic substance is mixed with Al2O3The mass ratio of the inorganic aluminum-containing compound is 0.1-20: 1, preferably 0.5 to 10: 1;
preferably, Al is used2O3The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite in a dry basis is 0.1-30: 100, preferably 1 to 20: 100, more preferably 5 to 15: 100, respectively;
preferably, the inorganic aluminum-containing compound is selected from at least one of aluminum sulfate, sodium metaaluminate, aluminum nitrate and aluminum trichloride.
5. Hydrodesulfurization catalyst according to any of claims 1 to 4, wherein the active component A is Co and/or Ni, preferably Co; the active component B is Mo and/or W, preferably Mo;
preferably, the content of the active component a is 0.4 to 4 wt.%, preferably 0.4 to 2.2 wt.%, and the content of the active component B is 2 to 8 wt.%, preferably 3.5 to 6 wt.%, calculated as oxide, based on the total amount of the hydrodesulfurization catalyst.
6. A process for preparing a gasoline selective hydrodesulfurization catalyst as defined in any one of claims 1 to 5 comprising:
the carrier is impregnated with a solution containing a precursor of active component a and a precursor of active component B, followed by drying and optionally calcination.
7. The preparation method according to claim 6, wherein the solution further contains a complexing agent selected from at least one of an organic acid and/or an ammonium salt thereof;
preferably, the organic acid is selected from at least one of trans-1, 2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid, and malic acid;
preferably, the mol ratio of the complexing agent to the active component A precursor calculated by the active component A is 0.3-2: 1.
8. the production method according to claim 6, wherein the drying conditions include: the temperature is 60-180 ℃, preferably 80-150 ℃; the time is 0.5 to 24 hours, preferably 3 to 12 hours;
preferably, the conditions of the calcination include: the temperature is 300-550 ℃, and preferably 400-500 ℃; the time is 0.5-15h, preferably 2-10 h.
9. Use of a catalyst according to any one of claims 1 to 5 for the selective hydrodesulfurization of gasoline.
10. A process for the selective hydrodesulfurization of gasoline, the process comprising: contacting a gasoline fraction, hydrogen and a gasoline selective hydrodesulfurization catalyst according to any one of claims 1 to 5 under gasoline selective hydrodesulfurization conditions.
11. The method of claim 10, wherein the gasoline selective hydrodesulfurization conditions comprise: the reaction temperature is 200 ℃ and 420 ℃, the pressure is 1-18MPa, and the volume space velocity is 0.3-10h-1The volume ratio of hydrogen to oil is 50-5000Nm3/m3；
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-1The volume ratio of hydrogen to oil is 200-1000Nm3/m3。
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