CN116060058A - Hydrodesulfurization catalyst suitable for low-pressure conditions and preparation method and application thereof - Google Patents

Hydrodesulfurization catalyst suitable for low-pressure conditions and preparation method and application thereof Download PDF

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Publication number
CN116060058A
CN116060058A CN202111273788.XA CN202111273788A CN116060058A CN 116060058 A CN116060058 A CN 116060058A CN 202111273788 A CN202111273788 A CN 202111273788A CN 116060058 A CN116060058 A CN 116060058A
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catalyst
acid
phosphorus
group
metal element
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CN116060058B (en
Inventor
陈文斌
刘清河
杨清河
习远兵
丁石
鞠雪艳
张润强
葛泮珠
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of catalysts, and discloses a hydrodesulfurization catalyst suitable for low-pressure conditions, and a preparation method and application thereof. A hydrodesulfurization catalyst suitable for use under low pressure conditions, the catalyst comprising at least one group VIII metal element, at least one group VIB metal element, phosphorus element, an alumina support and at least oneOrganic alcohol compounds and/or carboxylic acid compounds; wherein, P is 2 O 5 The phosphorus content of the catalyst is 2-10 wt%; wherein, the content of the VIB group metal element is 12 to 28 weight percent based on the total amount of the catalyst and calculated by oxide; wherein the atomic ratio of cobalt element in the VIII group metal element to the total VIII group metal element is not less than 0.8 in terms of element. The catalyst is particularly suitable for diesel hydrodesulfurization treatment under low pressure conditions, and shows excellent hydrodesulfurization performance in hydrodesulfurization reaction under low pressure conditions.

Description

Hydrodesulfurization catalyst suitable for low-pressure conditions and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrodesulfurization catalyst suitable for low-pressure conditions and a preparation method and application thereof.
Background
Along with the continuous increase of social environmental awareness, the quality standard of fuel is gradually improved, and clean diesel oil production technology is concerned by refineries. The use of advanced hydrodesulfurization catalysts is an economical and efficient means of upgrading diesel quality. In the diesel hydrogenation process, a great deal of hydrogen is consumed to carry out hydrodesulfurization and aromatic hydrocarbon saturation reactions. Under the trend of reducing carbon emission, reducing the consumption of hydrogen in the diesel hydrogenation reaction process becomes an important technical development direction. Generally, the operation pressure of the diesel hydrogenation reaction device is higher, generally 5-8MPa, and the aromatic hydrocarbon saturation reaction is easy to carry out, so that the hydrogen consumption is increased. Therefore, reducing the operating pressure of the apparatus has an extremely important role in reducing the reaction hydrogen consumption. However, most of the diesel hydrodesulfurization catalysts disclosed in the prior patent applications are suitable for higher reaction pressure conditions, such as those of application No. 201711023399.5 and 201110045663.1, and therefore, it is necessary to develop a diesel hydrodesulfurization catalyst suitable for use under low pressure conditions.
Aiming at the defects of the prior art, the hydrodesulfurization catalyst with excellent performance and suitable for low-pressure reaction conditions is prepared, has higher activity and stability, and can meet the requirements of clean diesel oil production.
Disclosure of Invention
The invention aims to solve the problem of poor stability of a hydrodesulfurization catalyst under low pressure conditions in the prior art, and provides a hydrodesulfurization catalyst suitable for low pressure conditions, a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a hydrodesulfurization catalyst suitable for use under low pressure conditions, the catalyst comprising at least one group VIII metal element, at least one group VIB metal element, a phosphorus element, an alumina carrier, and at least one organic alcohol compound and/or carboxylic acid compound; wherein, P is 2 O 5 The phosphorus content of the catalyst is 2-10 wt%; wherein, the content of the VIB group metal element is 12 to 28 weight percent based on the total amount of the catalyst and calculated by oxide; wherein the atomic ratio of cobalt element in the VIII group metal element to the total VIII group metal element is not less than 0.8 in terms of element.
Preferably, the alumina carrier contains phosphorus element.
In a second aspect, the present invention provides a process for preparing a hydrodesulphurisation catalyst suitable for use in low pressure conditions according to the first aspect, the process comprising: the method comprises the steps of introducing a VIII group metal precursor, a VIB group metal precursor, a phosphorus compound and an organic alcohol compound and/or a carboxylic acid compound into an alumina carrier by adopting an impregnation method, and then drying.
In a third aspect, the present invention provides the use of a hydrodesulphurisation catalyst according to the first aspect, suitable for use in the hydrofinishing of distillate oils.
The inventors have found in the study that, at a lower reaction pressure, the hydrogen in the reaction system is relatively insufficient, and in order to allow the hydrodesulfurization reaction to proceed smoothly, a hydrodesulfurization catalyst having higher activity and stability is generally required. According to the invention, the composition of the hydrodesulfurization catalyst is regulated and controlled by introducing phosphorus element and controlling the ratio of cobalt element in the VIII group metal element to the total amount of the VIII group metal element, so that the hydrodesulfurization catalyst with strong activity and stability and suitable for low-pressure conditions is provided.
In the invention, on one hand, the phosphorus element is introduced into the catalyst to reduce the alkaline center of the alumina carrier and increase the acid center, so that the interaction between the alumina carrier and the metal is weakened, and the dispersion of the active metal component is promoted. Preferably, part of phosphorus element is introduced into the alumina carrier, so that the loading effect of the active metal component on the alumina carrier is further improved, and the dispersity of the active metal component is improved. Meanwhile, the organic alcohol compound and/or carboxylic acid compound are introduced into the catalyst, so that the interaction between the carrier and the active center is weakened, the effect of the organic alcohol compound and/or carboxylic acid compound is better exerted under the condition that the phosphorus element on the surface of the alumina carrier exists, the dispersion of active components is better promoted by the organic alcohol compound and/or carboxylic acid compound, the hydrodesulfurization effect of the catalyst under low pressure is improved, the reaction efficiency is improved for clean production of diesel oil, and the catalyst has excellent industrial value.
Meanwhile, the preparation process of the hydrodesulfurization catalyst has low requirements on production equipment, low production cost and good practical value.
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 first aspect of the present invention provides a hydrodesulphurisation catalyst suitable for low pressure conditions, the catalyst comprising at least one group VIII metal element, at least one group VIB metal element, a phosphorus element, an alumina support and at least one organic alcohol compound and/or carboxylic acid compound; wherein, P is 2 O 5 The phosphorus content of the catalyst is 2-10 wt%; wherein, the content of the VIB group metal element is 12 to 28 weight percent based on the total amount of the catalyst and calculated by oxide; wherein the atomic ratio of cobalt element in the VIII group metal element to the total VIII group metal element is not less than 0.8 in terms of element.
In the present invention, there is provided a hydrodesulfurization catalyst having the above-mentioned specific composition and suitable for use under low pressure conditions, which has good activity and stability even under low pressure conditions, and is particularly suitable for use in hydrodesulfurization under low pressure conditions.
In the present invention, preferably, the group VIII metal element is cobalt and optionally one of other elements in the group VIII metal element. In a preferred case, the other elements of the group VIII metal element include, but are not limited to, at least one of iron, nickel and palladium, preferably nickel.
In the present invention, the selection range of the group VIB metal element is not particularly limited. Preferably, the group VIB metal element includes, but is not limited to, at least one of chromium, molybdenum, and tungsten, preferably molybdenum and/or tungsten.
In the invention, the amount of the group VIII metal element is not particularly limited as long as the performance of the hydrodesulfurization catalyst can be satisfied, and the amount of the active metal component in the hydrodesulfurization catalyst cannot be excessive, and the excessive active metal component can reduce the desulfurization activity of the catalyst and simultaneously reduce the stability of the catalyst. In a preferred case, the atomic ratio of cobalt element in the group VIII metal element to the total amount of the group VIII metal element is 0.85 to 1 in terms of element. The advantage of using such preferred embodiments is that when the cobalt content is within the above-described range, the hydrodesulfurization catalyst exhibits higher activity and stability under low pressure conditions, facilitating long-term operation of the catalyst.
In a preferred embodiment, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element is 0.1 to 0.35:1, preferably 0.2 to 0.3:1. the advantage of adopting this kind of preferred embodiment is that guarantee to keep good synergism between VIII group metal element and the VIB group metal element, and then improve the activity of catalyst for the catalyst keeps better stability under low pressure condition, guarantees long-period operation.
In the present invention, the phosphorus content in the catalyst is not particularly limited. Preferably in P 2 O 5 The phosphorus content of the catalyst is 3 to 10% by weight, more preferably 4 to 8% by weight. The adoption of the preferred embodiment can further promote the dispersion of the active metal component, better play the role of the active component, and the introduction of the phosphorus element can also enhance the acid function of the catalyst, thereby further improving the reaction effect of the catalyst under low pressure.
In the present invention, preferably, the phosphorus element in the catalyst contains two parts. Preferably, the alumina carrier contains a phosphorus element, hereinafter referred to as phosphorus-containing alumina. The advantage of using this preferred embodiment is that the presence of a specific amount of elemental phosphorus in the alumina support significantly promotes the activity of the catalyst under low pressure conditions.
In a preferred embodiment, in P 2 O 5 The phosphorus in the alumina support represents 10 to 40% by weight, preferably 10 to 35% by weight, of the total phosphorus content in the catalyst. The advantage of adopting this kind of preferred embodiment is that still further promotes the load effect of active metal component on the alumina support, promotes the dispersity of active metal component.
In the invention, the phosphorus element can be introduced into the formed alumina carrier, can be introduced in the forming process of the alumina carrier, and can also be introduced in the preparation process of the alumina carrier precursor. Preferably during the preparation of the alumina carrier precursor, when introduced during the preparation of the alumina precursor, phosphorus element may be introduced by adding a phosphorus-containing compound during the preparation of the alumina precursor using the aluminum sulfate-sodium metaaluminate method, specifically, phosphoric acid or phosphate is introduced as a raw material or at any step during the preparation of the alumina precursor. By introducing phosphorus element into the alumina precursor, the structural property of the alumina carrier is improved, and the dispersing capability of the active metal component is promoted.
In the present invention, the phosphorus element in the phosphorus-containing alumina carrier is provided by the alumina carrier precursor. In a preferred embodiment, the precursor of the alumina carrier is pseudo-boehmite, and the pseudo-boehmite contains phosphorus element.
Typically, sodium-containing precursors (e.g., sodium oxide) are used in the preparation of pseudo-boehmite, and such materials remain in the pseudo-boehmite. In a preferred embodiment, the sodium oxide content of the pseudo-boehmite is not more than 0.08% by weight, preferably not more than 0.06% by weight. The advantage of adopting this kind of preferred embodiment is that the content of sodium oxide in pseudo-boehmite is rationally controlled, further reduces the basic center, makes the catalyst have good activity and stability, promotes the hydrodesulfurization effect of the catalyst.
In the present invention, there is no particular limitation on the preparation method of the phosphorus-containing alumina carrier, and the conventional preparation methods in the art are applicable to the present invention. Preferably, the phosphorus-containing alumina carrier is prepared by extrusion molding, and the specific operation is not described herein.
In the present invention, in order to further improve the performance of the catalyst, a carrier having a specific composition and structure is selected as the carrier of the hydrodesulfurization catalyst. Preferably, the alumina carrier has a water absorption of greater than 0.9mL/g, more preferably 1-1.1mL/g, and a specific surface area of greater than 260m 2 Preferably from 260 to 350m 2 And/g, the average pore diameter is greater than 10nm, more preferably from 10 to 18nm.
In a preferred case, the alumina support has a pore volume with a pore size distribution of from 2 to 6nm of not more than 10%, preferably not more than 8%, more preferably from 5 to 8% of the total pore volume of the alumina support.
In a preferred case, the alumina support has a pore volume with a pore size distribution of from 2 to 4nm of not more than 4%, preferably not more than 2%, of the total pore volume of the alumina support.
The adoption of the preferential alumina carrier with specific composition and structure can ensure that the catalyst has a smoother pore canal structure, promote the reaction molecules to diffuse to the active center under low pressure, and further improve the activity and stability of the catalyst.
In the present invention, the specific surface area, pore volume, pore diameter and pore distribution of the carrier are measured by the low temperature nitrogen adsorption method (BET) (see "petrochemical analysis method (RIPP test method)", yang Cuiding et al, scientific Press, 1990). Wherein the pore volume of 2-100nm is calculated according to the BET result.
In the present invention, the amount of the organic alcohol compound and/or the carboxylic acid compound to be used is not particularly limited as long as the requirements of the hydrodesulfurization catalyst for use can be satisfied. Preferably, the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element is from 0.5 to 6:1, preferably 1-5:1. the advantage of using such preferred embodiments is that the organic alcohol compound and/or carboxylic acid compound can increase the dispersity of the active metal component, thereby increasing the initial activity and stability of the hydrodesulfurization catalyst.
In the present invention, the types of organic alcohol compounds are selected in a wide range, and organic alcohol compounds conventional in the art are suitable for use in the present invention. Preferably, the organic alcohol compound may be at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol. Further preferably, the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane, still further preferably at least one of glycerol, propanol and ethylene glycol.
In the present invention, the kind of the carboxylic acid compound is not particularly limited. Preferably, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, and further preferably at least one of formic acid, citric acid and acetic acid.
In the present invention, the size of the catalyst is not particularly limited. Preferably, the equivalent diameter of the catalyst is from 0.5 to 1.8mm, more preferably from 0.8 to 1.6mm.
In the present invention, the shape of the catalyst is not particularly limited, and the catalyst shape conventional in the art is applicable to the present invention. Preferably, the shape of the catalyst is cylindrical, clover, dished honeycomb or other irregular shape, further preferably butterfly.
In a second aspect, the present invention provides a process for preparing a hydrodesulphurisation catalyst suitable for use in low pressure conditions according to the first aspect, the process comprising: the method comprises the steps of introducing a VIII group metal precursor, a VIB group metal precursor, a phosphorus compound and an organic alcohol compound and/or a carboxylic acid compound into an alumina carrier by adopting an impregnation method, and then drying.
In the present invention, the types of the group VIII metal, the group VIB metal, and the organic alcohol compound and/or the carboxylic acid compound have been described in the first aspect, and will not be described herein.
In a preferred embodiment, preferably, the group VIB metal precursor includes, but is not limited to, one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, ammonium metatungstate, ammonium ethyl metatungstate, and tungsten oxide.
In a preferred embodiment, the group VIII metal precursor includes, but is not limited to, one or more of cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxide, nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide.
In a preferred embodiment, the phosphorus-containing compound includes, but is not limited to, one or more of phosphoric acid, hypophosphorous acid, ammonium phosphate, and monoammonium phosphate.
The impregnation method according to the present invention is not particularly limited, and any impregnation method conventional in the art is applicable to the present invention. For example, one of co-impregnation, stepwise impregnation, saturated impregnation and supersaturated impregnation may be used. In a preferred embodiment, the co-impregnation is used in the present invention to prepare a hydrodesulfurization catalyst suitable for use under low pressure conditions. In a more preferred embodiment, the impregnation method comprises: impregnating the alumina carrier with an impregnating solution containing a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and an organic alcohol compound and/or a carboxylic acid compound.
In the present invention, the order of addition of the group VIII metal precursor, the group VIB metal precursor, the phosphorus-containing compound, and the organic alcohol compound and/or the carboxylic acid compound is not particularly limited, as long as it is advantageous for uniform mixing of the components. In a preferred embodiment, the organic alcohol compound and/or carboxylic acid compound, the group VIII metal precursor, the group VIB metal precursor are added separately to an aqueous solution of a phosphorus-containing compound to provide the impregnation solution. In the present invention, the order of addition of the organic alcohol compound and/or carboxylic acid compound, phosphorus-containing compound, and metal precursor may be changed with each other.
In the invention, the hydrodesulfurization catalyst can be prepared by the following preparation method: firstly, dissolving a phosphorus-containing compound in water to obtain a phosphorus-containing aqueous solution, then adding an organic alcohol compound and/or a carboxylic acid compound, a VIB group metal precursor and a VIII group metal precursor, stirring under heating until the phosphorus-containing compound is completely dissolved, and keeping the temperature constant to obtain an impregnating solution, measuring the water absorption rate of an alumina carrier, and calculating the liquid absorption rate of the alumina carrier according to a formula of the water absorption rate-0.1 of the alumina carrier; according to the liquid absorption rate of the alumina carrier, the impregnating solution is fixed to a corresponding volume (the liquid absorption rate of the alumina carrier is multiplied by the mass of the carrier), and the impregnating solution and the alumina carrier with corresponding mass are uniformly mixed and kept stand, and then dried, so that the hydrodesulfurization catalyst applicable to the low-pressure condition is prepared.
In the present invention, the range of selection of the drying conditions is wide. Preferably, the drying conditions include: the temperature is 80-200deg.C, and the time is 1-10h.
In a third aspect, the invention provides the use of the hydrogenation catalyst for low pressure conditions as described in the first aspect in the hydrofinishing of distillate.
In a preferred case, the sulfur content in the distillate to be treated is not more than 13000ppm, preferably 3000-13000ppm.
In a preferred case, the catalyst is sulfided to convert the oxidation state catalyst to a sulfided state catalyst prior to use. In the present invention, the vulcanization method is not particularly limited, and any vulcanization method conventional in the art is applicable to the present invention. Preferably, for example, one of dry vulcanization and wet vulcanization is possible. The kind of the vulcanizing agent is not particularly limited, and may be selected according to a conventional scheme in the art.
Preferably, the vulcanization conditions include: the vulcanization temperature is 280-420 ℃, the time is 10-48 hours, the pressure is 0.1-15MPa, and the volume airspeed is 0.5-20 hours -1 The volume ratio of the hydrogen oil is 100-2000:1, preferably at a heating rate of 5-60 ℃/hr.
In a preferred case, the catalyst is used at a temperature of 320-400 ℃, the reaction pressure of 2-4.5MPa and the volume space velocity of 0.5-3 hours -1 The volume ratio of the hydrogen oil is 100-500:1.
the present invention will be described in detail by examples. In the following examples, the hydrodesulfurization performance of hydrodesulfurization catalysts suitable for use in low pressure conditions was measured on a small, high pressure reactor, and the oxidation state catalyst was first converted to a sulfided state catalyst using a temperature programmed sulfidation process. The vulcanization conditions are as follows: the vulcanization pressure is 6.4MPa, and the vulcanized oil contains CS 2 2% by weight kerosene, volume space velocity of 2 hours -1 The hydrogen-oil volume ratio is 300v/v, the constant temperature is kept for 6 hours at 230 ℃/h, then the temperature is raised to 360 ℃ for 8 hours of vulcanization, and the temperature raising rate of each stage is 10 ℃/h. After vulcanization, the reaction raw materials are switched to carry out hydrodesulfurization activity test, wherein the reaction raw materials are diesel raw materials with the sulfur content of 9870 ppm. The test conditions were: the pressure is 4.0MPa and the volume space velocity is 1.5 hours -1 The hydrogen-oil volume ratio was 300v/v and the reaction temperature was 360 ℃. The product properties were analyzed after 2 days of reaction stabilization. To examineThe stability of the catalyst is kept at 10ppm by the mass fraction of sulfur in the reaction product, the reaction temperature is regulated every day, the operation is continued for 5 days, the catalyst stability is represented by the difference value of the reaction temperature of the catalyst, and the lower the temperature raising value is, the better the catalyst stability is.
The composition of the catalyst is calculated according to the feeding amount. The specific surface area, pore distribution, pore volume and pore diameter of the pore diameter of 2-100nm in the carrier are measured by a low-temperature nitrogen adsorption method (see petrochemical analysis method (RIPP test method), code Yang Cuiding et al, scientific press, 1990 publication). The product was analyzed for sulfur mass fraction using a sulfur nitrogen analyzer (model TN/TS3000, available from Sieimer).
Example 1
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic cobalt carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is a phosphorus-containing alumina carrier, and the introduction of phosphorus element in the carrier is obtained by adding a certain amount of phosphoric acid into alumina for modification and roasting at 600 ℃ for 3 hours. The water absorption rate of the phosphorus-containing alumina carrier is 1.08mL/g, and the specific surface area is 275m 2 And/g, wherein the average pore diameter is 12.2nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5.2%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1.2%, and the pore diameter distribution is mainly concentrated at 8-20nm. In addition, the sodium oxide content of the support was 0.05% by weight.
MoO in the preparation of the catalyst 3 The content was 20 wt%, the atomic ratio Co/(Co+Mo) was 0.25, P 2 O 5 The content was 6 wt%, of which 30 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 7.8ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.7 ℃ after 5 days of reaction.
Example 2
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 3 hours until the basic cobalt carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is a phosphorus-containing alumina carrier, and the introduction of phosphorus element in the carrier is obtained by adding a certain amount of phosphoric acid into alumina for modification and roasting at 600 ℃ for 3 hours. The water absorption rate of the phosphorus-containing alumina carrier is 1.05mL/g, and the specific surface area is 269m 2 And/g, wherein the average pore diameter is 11.9nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 6.7%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1.9%, and the pore diameter distribution is mainly concentrated at 8-20nm. The sodium oxide content of the support was 0.03 wt%.
MoO in the preparation of the catalyst 3 The content was 15 wt%, the atomic ratio Co/(Co+Mo) was 0.3, P 2 O 5 The content is 8 wt%, wherein 20 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal was 2.5:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 9.8ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.8 ℃ after 5 days of reaction.
Example 3
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 4 hours until the basic cobalt carbonate, the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is a phosphorus-containing alumina carrier, wherein phosphorus element in the carrier is introduced by adding phosphoric acid in the preparation process of precursor pseudo-boehmite so as to prepare the phosphorus-containing alumina carrier, and the phosphorus-containing alumina carrier is obtained after roasting for 3 hours at 600 ℃. The water absorption rate of the phosphorus-containing alumina carrier is 1.02mL/g, and the specific surface area is 286m 2 And/g, wherein the average pore diameter is 11.2nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm. The sodium oxide content of the support was 0.06 wt.%.
In preparing the catalyst, moO 3 22 wt%, the atomic ratio of (Co+Ni)/(Co+Ni+Mo) was 0.3, the atomic ratio of Co/(Co+Ni) was 0.8, and P 2 O 5 The content is 5 wt%, wherein 25 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal was 1.5:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 9.0ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.7 ℃ after 5 days of reaction.
Example 4
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic cobalt carbonate, the basic nickel carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The support used to prepare the catalyst was the phosphorus-containing alumina support prepared in example 3.
MoO in the preparation of the catalyst 3 The content was 25 wt%, the atomic ratio of (Co+Ni)/(Co+Ni+Mo) was 0.27, the atomic ratio of Co/(Co+Ni) was 0.95, and P 2 O 5 The content was 4 wt%, wherein 10 wt% of P 2 O 5 From the carrier. The mole ratio of citric acid to group VIII metal is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 6.9ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.8 ℃ after 5 days of reaction.
Example 5
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate and citric acid into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic cobalt carbonate and the citric acid are completely dissolved, and obtaining impregnation solution containing active metals. Uniformly mixing the impregnating solution with the carrier, standing for 4h, and passing through a step 120Drying for 5 hours at the temperature of C, and preparing the catalyst with the particle size of 1.6mm and the shape of butterfly.
The support used to prepare the catalyst was the phosphorus-containing alumina support of example 3.
MoO in the preparation of the catalyst 3 The content was 18% by weight, the atomic ratio Co/(Co+Mo) was 0.3, P 2 O 5 The content was 9 wt%, of which 35 wt% of P 2 O 5 From the carrier. The mole ratio of citric acid to group VIII metal is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 8.9ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.9 ℃ after 5 days of reaction.
Example 6
Adding a certain amount of ammonium metatungstate, basic cobalt carbonate, basic nickel carbonate and citric acid into an aqueous solution containing phosphoric acid respectively, heating and stirring at 90 ℃ for 3 hours until the ammonium metatungstate, the basic cobalt carbonate, the basic nickel carbonate and the citric acid are completely dissolved, and obtaining an impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The catalyst was prepared using the phosphorus-containing alumina support of example 3.
WO in the preparation of the catalyst 3 The content was 25 wt%, the atomic ratio of (Co+Ni)/(Co+Ni+W) was 0.3, the atomic ratio of Co/(Co+Ni) was 0.95, and P 2 O 5 The content is 9 wt%, wherein, 15 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal was 1.5:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 7.0ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.0 ℃ after 5 days of reaction.
Example 7
A catalyst was prepared as in example 2, except that the sodium oxide in the alumina support was 0.13% by weight. After the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 15.5ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.9 ℃ after 5 days of reaction.
Example 8
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic cobalt carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is gamma-alumina carrier, the water absorption rate is 1.04mL/g, and the specific surface area is 270m 2 And/g, wherein the average pore diameter is 11.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm. The sodium oxide content of the support was 0.13% by weight.
MoO in the preparation of the catalyst 3 The content was 20% by weight, the atomic ratio Co/(Co+Mo) was 0.28, P 2 O 5 The content was 6 wt%, and the carrier contained no phosphorus element. The molar ratio of glycerol to group VIII metal is 5:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 18.0ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.3 ℃ after 5 days of reaction.
Example 9
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic cobalt carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly.
The carrier used for preparing the catalyst is a phosphorus-containing alumina carrier, and the pseudo-boehmite precursor used for preparing the carrier contains phosphorus element and is prepared by adding phosphoric acid as a raw material in the process of preparing the pseudo-boehmite precursor. The water absorption rate of the prepared phosphorus-containing alumina carrier is 1.03mL/g, and the specific surface area is 285m 2 And/g, wherein the average pore diameter is 11.8nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 6.5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1.2%, and the pore diameter distribution is mainly concentrated at 8-20nm. In addition, the sodium oxide content of the support was 0.05% by weight.
MoO in the preparation of the catalyst 3 The content was 20 wt%, the atomic ratio Co/(Co+Mo) was 0.25, P 2 O 5 The content was 6 wt%, of which 30 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 6.8ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 1.5 ℃ after 5 days of reaction.
Comparative example 1
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 85 ℃ for 3 hours until the basic cobalt carbonate, the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly. Comparative example 1 the phosphorus-containing alumina support of example 1 was selected.
MoO in the preparation of the catalyst 3 The content was 32 wt%, the atomic ratio of (Co+Ni)/(Co+Ni+Mo) was 0.18, the atomic ratio of Co/(Co+Ni) was 0.85, and P 2 O 5 The content is 6 wt%, wherein, 8 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to the group VIII metal element is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 32.0ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.3 ℃ after 5 days of reaction.
Comparative example 2
To a certain amount of MoO 3 Respectively adding basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly. Comparative example 2 the phosphorus containing alumina support of example 1 was selected.
MoO in the preparation of the catalyst 3 The content was 20 wt%, the Ni/(Ni+Mo) atomic ratio was 0.25, P 2 O 5 The content was 6 wt%, of which 15 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to the group VIII metal element is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 28.0ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.2 ℃ after 5 days of reaction.
Comparative example 3
To a certain amount of MoO 3 Respectively adding basic cobalt carbonate, basic nickel carbonate and glycerol into aqueous solution containing phosphoric acid, heating and stirring at 95 ℃ for 3 hours until the basic cobalt carbonate, the basic nickel carbonate and the glycerol are completely dissolved, and obtaining impregnation solution containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the impregnated solution is dried for 5 hours at 120 ℃ to prepare the catalyst with the particle size of 1.6mm and the shape of a butterfly. Comparative example 3 the phosphorus containing alumina support of example 1 was selected.
MoO in the preparation of the catalyst 3 The content was 20 wt%, the atomic ratio of (Co+Ni)/(Co+Ni+Mo) was 0.3, the atomic ratio of Co/(Co+Ni) was 0.5, and P 2 O 5 The content was 6 wt%, of which 15 wt% of P 2 O 5 From the carrier. The molar ratio of glycerol to group VIII metal is 1:1. after the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 26.5ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 2.9 ℃ after 5 days of reaction.
Comparative example 4
A catalyst was prepared according to the procedure of example 3, except that no organic alcohol compound was introduced during the preparation, and the catalyst was subjected to sulfidation and reaction tests to give a sulfur content of 42.6ppm in the product. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.6 ℃ after 5 days of reaction.
Comparative example 5
A catalyst was prepared according to the procedure of example 2, except that P 2 O 5 The phosphorus content of the catalyst was 1.2% by weight. After the catalyst is vulcanized and subjected to reaction test, the sulfur content in the product is 38.9ppm. When the sulfur content of the product is kept to be 10ppm, the reaction temperature is raised by 3.6 ℃ after 5 days of reaction.
The catalyst provided by the invention has higher activity and stability under the low-pressure reaction condition, has excellent hydrodesulfurization performance under the low-pressure reaction condition, and has good industrial application prospect.
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 (10)

1. A hydrodesulphurisation catalyst suitable for use in low pressure conditions, the catalyst comprising at least one group VIII metal element, at least one group VIB metal element, a phosphorus element, an alumina support and at least one organic alcohol compound and/or carboxylic acid compound; wherein, P is 2 O 5 The phosphorus content of the catalyst is 2-10 wt%;
wherein, the content of the VIB group metal element is 12 to 28 weight percent based on the total amount of the catalyst and calculated by oxide;
wherein the atomic ratio of cobalt element in the VIII group metal element to the total VIII group metal element is not less than 0.8 in terms of element.
2. The catalyst according to claim 1, wherein the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element is 0.1 to 0.35:1, preferably 0.2 to 0.3:1.
3. the catalyst according to claim 1, wherein, in P 2 O 5 The phosphorus content of the catalyst is 3-10 wt%;
preferably, the alumina carrier contains phosphorus element;
preferably in P 2 O 5 The phosphorus in the alumina carrier accounts for 10-40 wt%, preferably 10-35 wt%, of the total phosphorus content in the catalyst;
preferably, the precursor of the alumina carrier is pseudo-boehmite, and the pseudo-boehmite contains phosphorus element;
preferably, the sodium oxide content in the pseudo-boehmite is not more than 0.08% by weight, preferably not more than 0.06% by weight.
4. The catalyst of claim 1, wherein the alumina carrier has a water absorption of greater than 0.9mL/g and a specific surface area of greater than 260m 2 /g, average pore size greater than 10nm;
preferably, in the alumina carrier, the pore volume with the pore diameter distribution of 2-6nm accounts for no more than 10%, preferably no more than 8% of the total pore volume of the alumina carrier;
preferably, in the alumina support, the pore volume with a pore size distribution of from 2 to 4nm represents no more than 4%, preferably no more than 2%, of the total pore volume of the alumina support.
5. The catalyst according to claim 1, wherein the molar ratio of the organic alcohol compound and/or carboxylic acid compound to the group VIII metal element is 0.5 to 6:1, preferably 1-5:1, a step of;
preferably, the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane, preferably at least one of glycerol, propanol and ethylene glycol;
preferably, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, preferably at least one of formic acid, citric acid and acetic acid.
6. Catalyst according to any of claims 1-5, wherein the equivalent diameter of the catalyst is 0.5-1.8mm, preferably 0.8-1.6mm;
preferably, the shape of the catalyst is cylindrical, clover, butterfly, honeycomb or other irregular shape.
7. A process for preparing a hydrodesulfurization catalyst suitable for use under low pressure conditions as defined in any one of claims 1 to 6, which process comprises:
the method comprises the steps of introducing a VIII group metal precursor, a VIB group metal precursor, a phosphorus compound and an organic alcohol compound and/or a carboxylic acid compound into an alumina carrier by adopting an impregnation method, and then drying.
8. The production method according to claim 7, wherein the impregnation method comprises: impregnating the alumina with an impregnating solution containing a group VIII metal precursor, a group VIB metal precursor, a phosphorus-containing compound, and an organic alcohol compound and/or a carboxylic acid compound;
preferably, the organic alcohol compound and/or carboxylic acid compound, the group VIII metal precursor and the group VIB metal precursor are added to the aqueous solution of the phosphorus-containing compound respectively to provide the impregnation liquid;
preferably, the drying conditions include: the temperature is 80-200deg.C, and the time is 1-10h.
9. Use of a hydrodesulphurisation catalyst according to any of claims 1-6, suitable for low pressure conditions, in the hydrofinishing of distillate oils.
10. Use according to claim 9, wherein the catalyst is sulfided to a sulfided catalyst prior to use;
preferably, the catalyst is used at 320-400 deg.C, the reaction pressure is 2-4.5MPa and the volume space velocity is 0.5-3 hr -1 The volume ratio of the hydrogen oil is 100-500:1.
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