CN116196956A - Hydrogenation catalyst, preparation method and application thereof - Google Patents

Hydrogenation catalyst, preparation method and application thereof Download PDF

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Publication number
CN116196956A
CN116196956A CN202111444896.9A CN202111444896A CN116196956A CN 116196956 A CN116196956 A CN 116196956A CN 202111444896 A CN202111444896 A CN 202111444896A CN 116196956 A CN116196956 A CN 116196956A
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China
Prior art keywords
content
acid
oxygen
mesoporous carbon
carbon carrier
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CN202111444896.9A
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Inventor
李会峰
王薇
杨清河
张锐
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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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Priority to CN202111444896.9A priority Critical patent/CN116196956A/en
Publication of CN116196956A publication Critical patent/CN116196956A/en
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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
    • B01J27/24—Nitrogen 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
    • 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
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a hydrogenation catalyst and a preparation method and application thereof, wherein the catalyst comprises a mesoporous carbon carrier and an active metal component loaded on the mesoporous carbon carrier; the mesoporous carbon carrier contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element. The preparation method of the hydrogenation catalyst comprises the steps of preparing a mesoporous carbon carrier and introducing hydrogenation active metal into the mesoporous carbon carrier; the mesoporous carbon carrier preparation method comprises the following steps: and uniformly mixing the carbon carrier precursor, the phosphorus source and the binder to obtain a mixed material, and performing heat treatment on the mixed material in an oxygen-containing atmosphere. The preparation method of the mesoporous carbon carrier has the advantages of simple process flow and good environmental protection, and is suitable for industrial mass production of the carbon carrier. Compared with the catalyst prepared by the prior art, the hydrogenation catalyst provided by the invention has higher hydrogenation activity when being used for the hydrotreating of petroleum fractions and residual oil and the hydrogenation process of chemical raw materials and products.

Description

Hydrogenation catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a hydrogenation catalyst containing a mesoporous carbon carrier, and a preparation method and application thereof.
Background
The hydrogenation catalyst prepared by the carbon carrier has weaker interaction between the carbon carrier and the metal component, which is beneficial to improving the hydrogenation activity of the catalyst, and the waste catalyst can conveniently recover the metal by a carrier burning method, so the application of the carbon material as the carrier has been attracting attention, in particular to the mesoporous carbon material carrier.
At present, the synthesis of mesoporous carbon materials mainly comprises two methods, namely a hard template method and a soft template method. 93120049.0A process for preparing activated carbon, especially the process for preparing activated carbon from asphalt, features that the crushed asphalt is uniformly mixed with extrusion aid and adhesive; after anti-melting, carbonization and activation treatment, the active carbon product can be obtained. 201710172091.0A porous carbon and its preparation method are provided. The preparation method of the porous carbon comprises the following steps: mixing coal liquefied asphalt, tetraethyl orthosilicate, hydrochloric acid and an organic solvent to prepare composite slurry; drying the composite slurry to obtain a composite; carbonizing the compound to obtain a carbonized substance; and removing silicon dioxide in the carbide to obtain the porous carbon. The step of removing silica from the char comprises: and soaking the carbide in NaOH aqueous solution or hydrofluoric acid for 12-24 hours to obtain the porous carbon.
The preparation process is relatively complex, and acid washing or alkali washing is needed in the process, so that a certain amount of waste liquid can be generated; or an organic template agent is needed, and the cost of raw materials is relatively high. Therefore, a technology which is simple in process flow and low in cost and is very suitable for industrial large-scale application is needed to prepare the mesoporous carbon material, and then the mesoporous carbon material is used as a carrier to prepare the supported hydrogenation catalyst.
Disclosure of Invention
The invention aims to provide a hydrogenation catalyst taking mesoporous carbon material as a carrier, a preparation method of the hydrogenation catalyst and application of the hydrogenation catalyst in hydrocarbon oil hydrogenation treatment, and particularly the invention comprises the following matters.
The invention provides a hydrogenation catalyst, which comprises a mesoporous carbon carrier and an active metal component loaded on the mesoporous carbon carrier, wherein the active metal component comprises at least one metal element of VIII family and at least one metal element of VIB family; the mesoporous carbon carrier contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 80-90 wt%, the content of the oxygen element is 2-6 wt%, the content of the hydrogen element is 0.1-1 wt%, the content of the sulfur element is 1-8 wt%, the content of the nitrogen element is 0.5-3 wt%, and the content of the phosphorus element is 0.5-10 wt%, based on the total weight of the mesoporous carbon carrier.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the steps of preparing a mesoporous carbon carrier and introducing at least one VIII group metal element and at least one VIB group metal element into the mesoporous carbon carrier; the mesoporous carbon carrier contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 80-90 wt%, the content of the oxygen element is 2-6 wt%, the content of the hydrogen element is 0.1-1 wt%, the content of the sulfur element is 1-8 wt%, the content of the nitrogen element is 0.5-3 wt%, and the content of the phosphorus element is 0.5-10 wt%, based on the total weight of the mesoporous carbon carrier; wherein, the mesoporous carbon carrier preparation steps include: (1) Uniformly mixing a carbon carrier precursor, a phosphorus source and an adhesive to obtain a mixed material, wherein the carbon carrier precursor is asphalt powder and/or petroleum coke powder, the phosphorus source is a phosphorus-containing compound, and the phosphorus-containing compound comprises at least one of phosphoric acid, phosphate or a phosphorus-containing organic compound; (2) Carrying out heat treatment on the mixed material in an oxygen-containing atmosphere; the phosphorus source is used in an amount of 0.5 to 8 parts by weight, preferably 1 to 6 parts by weight, based on phosphorus pentoxide, relative to 100 parts by weight of the asphalt powder and/or petroleum coke powder; the binder is used in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight.
The invention also provides the application of the hydrogenation catalyst provided by the invention or the hydrogenation catalyst prepared by any one of the methods provided by the invention in the hydrocarbon oil hydrogenation treatment.
Compared with the catalyst prepared by the prior art, the catalyst provided by the invention has higher hydrogenation activity when being used for the hydrogenation process of petroleum fractions and residual oil and chemical raw materials and products.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
According to the hydrogenation catalyst provided by the invention, the types and the contents of the hydrogenation active metal elements are selected conventionally in the field, generally, the VIII group metal element can be cobalt and/or nickel, and the VIB group metal element can be molybdenum and/or tungsten; preferably, the content of the mesoporous carbon carrier is preferably 50-95 wt% based on the total catalyst, the content of the group VIII metal element is 0.5-10 wt% based on oxide, and the content of the group VIB metal element is 4-40 wt%; based on the total weight of the mesoporous carbon carrier, the content of the carbon element is 82-88 wt%, the content of the oxygen element is 3-5 wt%, the content of the hydrogen element is 0.2-0.8 wt%, the content of the sulfur element is 2-6 wt%, the content of the nitrogen element is 1-2.5 wt%, and the content of the phosphorus element is 1-6 wt%, based on the total weight of the mesoporous carbon carrier.
The carbon carrier is a mesoporous material, has larger accessible pore diameter which can reach more than 6nm, and generally has accessible pore diameter of 2-30 nm, preferably 6-20 nm. The invention has no special requirement on the specific surface area and pore volume of the carbon carrier, for example, the specific surface area can be 50-1200 m 2 Preferably 100 to 1000m 2 /g; the pore volume can be 0.3-1.3 cm 3 Preferably 0.4 to 1.2cm per gram 3 /g。
According to the present invention, the hydrogenation catalyst preferably contains an organic auxiliary agent, the organic auxiliary agent may be at least one selected from the group consisting of an organic acid and/or an ammonium salt thereof, an organic alcohol and a saccharide compound, and the molar ratio of the organic auxiliary agent to the first active metal element may be (0.3 to 2): 1. The organic aid can enable the active element components to be uniformly dispersed in the porous carbon carrier, so that the hydrogenation activity of the hydrogenation catalyst is further improved. Further preferably, the organic acid is selected from at least one of trans 1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; the organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; the saccharide compound is at least one selected from the group consisting of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.
According to the invention, the catalyst may also contain non-metallic promoters which promote the catalytic properties, such as phosphorus promoters, boron promoters, etc., which, in addition to the phosphorus contained in the support, may originate from the incorporation together with impregnation of the active metal and/or organic promoter, the content of promoter being selected conventionally, for example based on the weight of the catalyst and based on P 2 O 5 The phosphorus content is from 0.5 to 10% by weight, preferably from 1 to 8% by weight, based on B 2 O 3 The boron content is 0.5 to 10% by weight, preferably 1 to 8% by weight.
According to the preparation method of the hydrogenation catalyst provided by the invention, preferably, the total weight of the mesoporous carbon carrier is taken as a reference, the content of the carbon element is 82-88 wt%, the content of the oxygen element is 3-5 wt%, the content of the hydrogen element is 0.2-0.8 wt%, the content of the sulfur element is 2-6 wt%, the content of the nitrogen element is 1-2.5 wt%, and the content of the phosphorus element is 1-6 wt%. Preferably, the VIII metal element is cobalt and/or nickel, the VIB metal element is molybdenum and/or tungsten, the content of each component is 59-94 wt% of the mesoporous carbon carrier based on the total catalyst, the content of the VIII metal element calculated by oxide is 1-6 wt% and the content of the VIB metal element is 5-35 wt%. According to the requirement, non-metal can be introduced in the catalyst preparation processAuxiliary agents such as auxiliary agents phosphorus, boron, and the like. Non-metallic adjuvants may be incorporated with the active metal and/or organic adjuvants. The amount of non-metal auxiliary introduced is not particularly limited, for example, such that phosphorus is present as P based on the total amount of catalyst 2 O 5 In an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight, based on B 2 O 3 The boron content is 0.5 to 10% by weight, preferably 1 to 8% by weight.
According to the invention, pitch powder and/or petroleum coke powder may be used as the carbon support precursor, or may be used as the precursor after each of them has been subjected to oxygen heat treatment (oxygen heat treatment). Specifically, petroleum coke is a product obtained by thermal cracking of heavy oil obtained by crude oil distillation. The thermal product of asphalt powder or petroleum coke powder refers to the product obtained by the thermal treatment of asphalt powder or petroleum coke powder in oxygen-containing atmosphere. Wherein, the conditions of the oxygen heat treatment may include: the flow rate of the oxygen-containing gas flow is 1-80 liters/hour, the temperature rising rate is 0.1-10 ℃/min, the oxygen heat treatment temperature is 120-450 ℃, and the oxygen heat treatment time is 1-48 hours.
The phosphorus source may be converted to phosphorus pentoxide during the heat treatment, which may contain small amounts of other impurity elements, such as small amounts of metal elements, in addition to C, H, O and P elements. Wherein the phosphate may be, for example, potassium, sodium or ammonium salts of phosphoric acid.
In the preparation method of the carbon carrier, the carbon carrier precursor and the phosphorus source are uniformly mixed under the action of the adhesive, and then the mesoporous carbon carrier is obtained through heat treatment, and the carbon carrier precursor and the phosphorus source are cheap raw materials, and a high-cost organic template agent is not required to be used in the preparation process, so that the preparation method of the invention has the advantage of low cost; moreover, the method does not involve the dissolving process of the template agent, and successfully avoids the use of the solvent with poor environmental protection to dissolve the template agent, so the method also has the advantages of simple process flow and good environmental protection, and is suitable for industrial mass production of the carbon carrier.
According to the present invention, the amounts of carbon in the precursor, the phosphorus source and the binder may vary within a range, for example, the phosphorus source may be used in an amount of 0.5 to 8 parts by weight, preferably 1 to 6 parts by weight, in terms of phosphorus pentoxide, relative to 100 parts by weight of the carbon support precursor; the binder may be used in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight.
In order to allow for a faster and better mixing of the materials, the carbon support precursor, the phosphorus source, may preferably have a smaller particle size, for example, the carbon support precursor may have a particle size of 1 to 1000 μm, preferably 1 to 250 μm. In order to further improve the uniformity of mixing, when the carbon support precursor, the phosphorus source and the binder are mixed uniformly, the binder may be impregnated with an aqueous solution of the phosphorus source first, and then the carbon support precursor is added and stirred uniformly.
According to the invention, the binder may comprise at least one of a cellulose ether, a starch or an enol polymer, preferably a cellulose ether, more preferably at least one of methylcellulose, hydroxyethyl methylcellulose or hydroxypropyl methylcellulose.
According to the present invention, the asphalt powder may be selected within a certain range, for example, the asphalt powder may include petroleum asphalt powder and/or coal asphalt powder, and the asphalt powder may contain polycyclic aromatic hydrocarbon, and the polycyclic aromatic hydrocarbon may be contained in an amount of 70 to 100 wt%, preferably 85 to 100 wt%, based on the total weight of the asphalt powder.
According to the invention, the heat treatment of the mixture under an oxygen-containing atmosphere to obtain the mesoporous carbon carrier may include: in an oxygen-containing atmosphere, the temperature of the mixed material is raised to 120-450 ℃ from room temperature according to the heating rate of 0.1-10 ℃/min, and the first heat treatment is carried out for 0.1-48 hours, so as to obtain an intermediate product; and in an oxygen-containing atmosphere, the temperature of the intermediate product is increased to 700-1000 ℃ according to the heating rate of 0.1-10 ℃/min, and the second heat treatment is carried out for 0.1-12 hours, so as to obtain the mesoporous carbon carrier. Wherein the oxygen-containing atmosphere contains oxygen-containing gas or mixed gas of oxygen-containing gas and inert gas, and the oxygen-containing gas comprises at least one of oxygen, carbon dioxide and carbon monoxide; the inert gas includes at least one of nitrogen, argon and helium. Further, the flow rate of the oxygen-containing gas stream at the time of the first heat treatment may be 0.1 to 80 liters/hour, and the flow rate of the oxygen-containing gas stream at the time of the second heat treatment may be 0.1 to 80 liters/hour.
In the invention, any means in the prior art can be adopted to load hydrogenation active metal onto a carbon carrier, preferably an impregnation method is adopted, specifically, the hydrogenation active metal is prepared into an aqueous solution, then the carbon carrier is impregnated, and the hydrogenation catalyst is obtained after drying. The content of the carbon carrier and the active metal in the finally obtained hydrogenation catalyst meets the requirements of the invention on the components by using the components. According to the method for preparing the hydrogenation catalyst provided by the invention, when the catalyst contains the organic auxiliary agent, the preparation method correspondingly comprises the step of introducing the organic auxiliary agent. The organic auxiliary agent can be introduced onto the carrier simultaneously with the hydrogenation active component, or can be introduced before or after the hydrogenation active metal is introduced. When a separate introduction scheme is employed, each introduction may be followed by an appropriate drying treatment. Preferably, the organic auxiliary agent is selected from at least one of organic acid and/or ammonium salt thereof, organic alcohol and saccharide compound, and the molar ratio of the organic auxiliary agent to the VIII group metal element is (0.3-2): 1; the organic acid is at least one of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; the organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; the saccharide compound is at least one selected from the group consisting of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.
Finally, according to the application of the catalyst provided by the invention in the hydrocarbon oil hydrogenation treatment, the hydrogenation catalyst is generally vulcanized and then subjected to the hydrogenation treatment. In particular, hydrocarbon oil feedstock may be contacted with the catalyst of the present invention or a catalyst prepared by the process of the present invention under hydrotreating conditions which are conventional conditions. For example: pressure of0.2-14MPa, hydrogen-oil volume ratio of 50-500:1, volume airspeed of 1-8h -1 The temperature is 200-400 ℃ and the time is 2-12 hours.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby. The materials, reagents, instruments and equipment involved in the embodiments of the present disclosure, unless otherwise specified, are all available commercially.
Petroleum coke powder oxygen thermal product SYJ-450 powder: petroleum coke is placed in a muffle furnace, air is introduced, the flow rate is controlled to be 80 liters/hour, the temperature of the mixed material is raised to 450 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 450 ℃ for 4 hours, and the obtained product is crushed to obtain SYJ-450 powder.
Petroleum coke powder oxygen thermal product SYJ-400 powder: petroleum coke is placed in a muffle furnace, air is introduced, the flow rate is controlled to be 80 liters/hour, the temperature of the mixed material is raised to 400 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 400 ℃ for 4 hours, and the obtained product is crushed to obtain SYJ-400 powder.
Petroleum coke breeze oxygen heat product SYJ-350 powder: petroleum coke is placed in a muffle furnace, air is introduced, the flow rate is controlled to be 80 liters/hour, the temperature of the mixed material is raised to 350 ℃ at the heating rate of 5 ℃/min, the mixed material is kept at the constant temperature of 350 ℃ for heat treatment for 4 hours, and the obtained product is crushed to obtain SYJ-350 powder.
Asphalt powder oxygen thermal product LQ-350 powder: placing asphalt in a muffle furnace, introducing air, controlling the flow to be 80 liters/hour, heating the mixed material to 350 ℃ at a heating rate of 5 ℃/minute, and keeping the constant temperature of 350 ℃ for heat treatment for 4 hours, and crushing the obtained product to obtain LQ-350 powder.
Asphalt powder oxygen thermal product LQ-300 powder: placing asphalt in a muffle furnace, introducing air, controlling the flow to be 80 liters/hour, heating the mixed material to 300 ℃ at the heating rate of 5 ℃/minute, keeping the constant temperature of 300 ℃ for heat treatment for 4 hours, and crushing the obtained product to obtain LQ-300 powder.
Preparation example 1
50 g of methyl cellulose is soaked in 200 ml of water solution containing 30 g of phosphoric acid (mass fraction is 85%), stirred, kept stand for 2 hours, then 500 g of asphalt powder is added, and stirred and mixed uniformly to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 360 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain a mesoporous carbon support S1.
In this preparation example, the amount of the phosphorus source (phosphoric acid) used was 3.69 parts by weight and the amount of the binder (methylcellulose) used was 10 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
The mesoporous carbon carrier S1 contains the carbon element, the oxygen element, the hydrogen element, the sulfur element, the nitrogen element and the phosphorus element, wherein the content of the carbon element is 82.16 weight percent, the content of the oxygen element is 4.47 weight percent, the content of the hydrogen element is 0.49 weight percent, the content of the sulfur element is 6.00 weight percent, the content of the nitrogen element is 1.47 weight percent and the content of the phosphorus element is 5.41 weight percent based on the total weight of the mesoporous carbon carrier S1.
Preparation example 2
50 g of methyl cellulose is immersed in 200 ml of aqueous solution containing 10 g of phosphoric acid (mass fraction 85%), stirred, and then allowed to stand for 2 hours, and then 500 g of asphalt powder is added, and stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow rate is controlled to be 40 liters/hour, the temperature of the mixture is increased to 240 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 240 ℃ for 18 hours, and then the temperature is increased to 340 ℃ at 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 950 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 950 ℃ for 4 hours, to obtain a mesoporous carbon support S2.
In this preparation example, the amount of the phosphorus source (phosphoric acid) was 2 parts by weight and the amount of the binder (methylcellulose) was 10 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
The S2 contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the total weight of the mesoporous carbon carrier S2 is taken as a reference, the content of the carbon element is 86.58 weight percent, the content of the oxygen element is 3.78 weight percent, the content of the hydrogen element is 0.52 weight percent, the content of the sulfur element is 5.57 weight percent, the content of the nitrogen element is 1.62 weight percent, and the content of the phosphorus element is 1.93 weight percent.
Preparation example 3
A mixture of 60 g of methyl cellulose, 20 g of hydroxyethyl methyl cellulose and 20 g of hydroxypropyl methyl cellulose is immersed in 200 ml of an aqueous solution containing 21g of phosphoric acid (mass fraction 85%), and after being stirred uniformly, the mixture is left to stand for 2 hours, and then 500 g of asphalt powder is added, and the mixture is stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow rate is controlled to be 40 liters/hour, the temperature of the mixture is increased to 350 ℃ at the heating rate of 5 ℃/min, and the mixture is kept at the constant temperature of 350 ℃ for heat treatment for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 6 hours, to obtain a mesoporous carbon support S3.
In this preparation example, the amount of the phosphorus source (phosphoric acid) was 4.2 parts by weight and the amount of the binder (methylcellulose+hydroxyethylmethyl cellulose+hydroxypropylmethyl cellulose) was 10 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
The S3 contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 87.72 weight percent, the content of the oxygen element is 2.81 weight percent, the content of the hydrogen element is 0.37 weight percent, the content of the sulfur element is 4.51 weight percent, the content of the nitrogen element is 1.52 weight percent and the content of the phosphorus element is 3.07 weight percent based on the total weight of the mesoporous carbon carrier S3.
Preparation example 4
Carbon support S4 was prepared according to the method of preparation example 1, except that: in this preparation example, the amount of the phosphorus source (phosphoric acid) was 0.5 part by weight and the amount of the binder (methylcellulose) was 1 part by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
Preparation example 5
Carbon support S5 was prepared according to the method of preparation example 1, except that: in this preparation example, the amount of the phosphorus source (sodium phosphate) was 8 parts by weight and the amount of the binder (starch) was 20 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
Preparation example 6
Carbon support S6 was prepared according to the method of preparation example 1, except that: in this preparation example, the amount of the phosphorus source (potassium phosphate) was 1 part by weight and the amount of the binder (enol polymer) was 5 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
Preparation example 7
Carbon support S7 was prepared according to the method of preparation example 1, except that: in this preparation example, the amount of the phosphorus source (ammonium phosphate) was 6 parts by weight and the amount of the binder (methylcellulose) was 15 parts by weight, based on 100 parts by weight of the asphalt powder, per phosphorus pentoxide.
Preparation example 8
50 g of methyl cellulose is soaked in 200 ml of water solution containing 30 g of phosphoric acid (mass fraction 85%), stirred and then kept stand for 2 hours, and then 200 g of petroleum coke powder, 100 g of asphalt powder, 20 g of SYJ-450 powder, 50 g of SYJ-400 powder, 30 g of SYJ-350 powder, 50 g of LQ-350 powder and 50 g of LQ-300 powder are added and stirred and mixed uniformly to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 400 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain a mesoporous carbon support S8.
In this production example, the amount of the phosphorus source (phosphoric acid) used was 3.69 parts by weight and the amount of the binder (methylcellulose) used was 10 parts by weight, based on 100 parts by weight of the carbon source, per phosphorus pentoxide. The S8 contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 87.59 weight percent, the content of the oxygen element is 2.51 weight percent, the content of the hydrogen element is 0.37 weight percent, the content of the sulfur element is 4.09 weight percent, the content of the nitrogen element is 2.28 weight percent and the content of the phosphorus element is 3.16 weight percent based on the total weight of the mesoporous carbon carrier S8.
Preparation example 9
50 g of methyl cellulose is soaked in 200 ml of water solution containing 35 g of phosphoric acid (mass fraction 85%), stirred and then kept stand for 2 hours, and then 400 g of asphalt powder, 10 g of SYJ-450 powder, 80 g of SYJ-400 powder and 10 g of SYJ-350 powder are added and stirred and mixed uniformly to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the temperature is increased to 350 ℃ at 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 940 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment at 940 ℃ was maintained for 4 hours, to obtain a mesoporous carbon support S9.
In this production example, the amount of the phosphorus source (phosphoric acid) used was 4.31 parts by weight and the amount of the binder (methylcellulose) used was 10 parts by weight, based on 100 parts by weight of the carbon source, per phosphorus pentoxide. The S9 contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the total weight of the mesoporous carbon carrier S9 is taken as a reference, the content of the carbon element is 87.36 weight percent, the content of the oxygen element is 2.40 weight percent, the content of the hydrogen element is 0.40 weight percent, the content of the sulfur element is 5.03 weight percent, the content of the nitrogen element is 1.68 weight percent, and the content of the phosphorus element is 3.13 weight percent.
Preparation example 10
50 g of methyl cellulose is soaked in 200 ml of water solution containing 30 g of phosphoric acid (mass fraction is 85%), stirred, kept stand for 2 hours, then 500 g of petroleum coke powder is added, and stirred and mixed uniformly to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 400 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain a mesoporous carbon support S10.
In this preparation example, the amount of the phosphorus source (phosphoric acid) used was 3.69 parts by weight and the amount of the binder (methylcellulose) used was 10 parts by weight, based on 100 parts by weight of petroleum coke powder, per phosphorus pentoxide. The mesoporous carbon carrier S10 contains the carbon element, the oxygen element, the hydrogen element, the sulfur element, the nitrogen element and the phosphorus element, wherein the content of the carbon element is 87.91 weight percent, the content of the oxygen element is 2.29 weight percent, the content of the hydrogen element is 0.33 weight percent, the content of the sulfur element is 4.35 weight percent, the content of the nitrogen element is 2.36 weight percent and the content of the phosphorus element is 2.76 weight percent based on the total weight of the mesoporous carbon carrier S10.
Preparation of comparative example 1
50 g of methyl cellulose is immersed in 200 ml of water, stirred uniformly, then kept stand for 2 hours, and 500 g of asphalt powder is added and stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 360 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-1.
Preparation of comparative example 2
50 g of methyl cellulose is immersed in 200 ml of aqueous solution containing 30 g of phosphoric acid (mass fraction 85%), and after uniform stirring, the mixture is left to stand for 2 hours, and then 500 g of asphalt powder is added and stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 360 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to nitrogen and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-2.
Preparation of comparative example 3
200 ml of an aqueous solution containing 30 g of phosphoric acid (85% by mass) was used to impregnate 500 g of asphalt powder, and the mixture was stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 360 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-3.
Preparation of comparative example 4
50 g of methyl cellulose is immersed in 200 ml of water, stirred, then kept stand for 2 hours, and then 500 g of petroleum coke powder is added, stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 400 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-4.
Preparation of comparative example 5
50 g of methyl cellulose is immersed in 200 ml of aqueous solution containing 30 g of phosphoric acid (mass fraction 85%), stirred, and then allowed to stand for 2 hours, and then 500 g of petroleum coke powder is added, stirred and mixed to obtain a mixed material. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 400 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to nitrogen and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-5.
Preparation of comparative example 6
200 ml of an aqueous solution containing 30 g of phosphoric acid (mass fraction 85%) was used to impregnate 500 g of petroleum coke powder, and the mixture was obtained by stirring and mixing. 200 g of the mixture is placed in a closed tube furnace, air is introduced and the flow is controlled to be 40 liters/hour, the temperature of the mixture is increased to 120 ℃ at the heating rate of 5 ℃/min, the constant temperature heat treatment is kept at 120 ℃ for 32 hours, and then the mixture is increased to 400 ℃ at the constant temperature of 1 ℃/min for 4 hours, so that an intermediate product is obtained; then, air was switched to carbon dioxide gas and the flow rate was controlled to 40 liters/hour, the temperature of the intermediate product was raised to 960 ℃ at a temperature raising rate of 5 ℃/minute, and the constant temperature heat treatment was maintained at 960 ℃ for 4 hours, to obtain the product DT-6.
Test case
Pore structure measurement was performed on each of the products produced in production examples 1 to 10 and production comparative examples 1 to 6, and the measurement results are shown in Table 1.
TABLE 1
Product(s) Ke Ji aperture (nm) Specific surface area (m) 2 /g) Pore volume (cm) 3 /g)
S1 10 386 0.51
S2 8 280 0.52
S3 11 285 0.51
S4 6 156 0.32
S5 19 259 0.50
S6 7 228 0.45
S7 17 267 0.53
S8 15 488 0.68
S9 12 353 0.45
S10 16 369 0.65
DT-1 2 6 0.01
DT-2 2 42 0.02
DT-3 3 15 0.02
DT-4 2 85 0.05
DT-5 2 1 0.01
DT-6 3 72 0.11
As can be seen from Table 1, the mesoporous carbon support obtained in the preparation example has a larger several pore diameter (6 nm or more), and the hydrogenation catalyst is prepared from the carbon support obtained in the above preparation example and the preparation comparative example.
Examples 1 to 10
200 g of the S1-S10 carbon support obtained in the above manner was impregnated with 170mL of an aqueous solution containing 3.98g of phosphoric acid (85%), 42.12g of molybdenum trioxide, 17.21g of basic nickel carbonate (NiO content: 51%), 22.56g of citric acid, 2.29g of ethylene glycol and 3.62g of glycerol, and after stirring uniformly, it was allowed to stand for 2 hours and dried at 120℃for 4 hours, to obtain catalyst C1-10.
Comparative examples 1 to 6
A comparative agent was prepared in the same manner as in example except that the carbon support was the supports DT-1 to DT-6 obtained in comparative preparation examples 1 to 6, and the obtained comparative agent was designated DC1 to DC6.
Evaluation of catalyst Performance
The hydrodesulfurization activity of catalysts C1 to C10 and DC1 to DC6 was evaluated using straight run kerosene (total sulfur 869. Mu.g/g) as a reaction raw material.
The evaluation device is a fixed bed hydrogenation reactor, the particle size of the catalyst is 20-30 meshes, and the catalyst dosage is 30ml. The hydrogen gas adopts one pass. Before the reaction, the catalyst is first presulfided, and the vulcanized oil contains 2% CS 2 Straight run kerosene. The vulcanization conditions are: pressure 1.6MPa, hydrogen-oil volume ratio 100:1, volume space velocity 4h -1 The temperature was 300℃for 4 hours. After sulfiding, the feed was switched to straight run kerosene, and the reaction conditions included: the reaction temperature is 240 ℃ and the volume space velocity is 4h -1 The reaction pressure is 1.6MPa, and the hydrogen-oil ratio is 100:1. After 6 days of reaction at 240 ℃, the samples were analyzed and the results are shown in table 2.
TABLE 2
Figure BDA0003384632630000161
Figure BDA0003384632630000171
Compared with a contrast agent, the catalyst provided by the invention has higher hydrodesulfurization activity.

Claims (12)

1. A hydrogenation catalyst comprising a mesoporous carbon support, an active metal component supported on the mesoporous carbon support, the active metal component comprising at least one group VIII metal element and at least one group VIB metal element; the mesoporous carbon carrier contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 80-90 wt%, the content of the oxygen element is 2-6 wt%, the content of the hydrogen element is 0.1-1 wt%, the content of the sulfur element is 1-8 wt%, the content of the nitrogen element is 0.5-3 wt%, and the content of the phosphorus element is 0.5-10 wt%, based on the total weight of the mesoporous carbon carrier.
2. The hydrogenation catalyst according to claim 1, wherein the group VIII metal element is cobalt and/or nickel, the group VIB metal element is molybdenum and/or tungsten, the mesoporous carbon support content is 50-95 wt% based on the total catalyst amount, the group VIII metal element content is 0.5-10 wt% based on oxide, and the group VIB metal element content is 4-40 wt%; based on the total weight of the mesoporous carbon carrier, the content of the carbon element is 82-88 wt%, the content of the oxygen element is 3-5 wt%, the content of the hydrogen element is 0.2-0.8 wt%, the content of the sulfur element is 2-6 wt%, the content of the nitrogen element is 1-2.5 wt%, and the content of the phosphorus element is 1-6 wt%, based on the total weight of the mesoporous carbon carrier.
3. The hydrogenation catalyst according to claim 1, wherein the mesoporous carbon support has a specific surface area of 50 to 1200m 2 Preferably 100 to 1000m 2 /g; pore volume is 0.3-1.3 cm 3 Preferably 0.4 to 1.2cm per gram 3 /g; the pore size may be from 2 to 30nm, preferably from 6 to 20nm.
4. The hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst contains an organic additive selected from at least one of an organic acid and/or an ammonium salt thereof, an organic alcohol and a saccharide compound, and the molar ratio of the organic additive to the group VIII metal element is (0.3-2): 1; the organic acid is at least one of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; the organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; the saccharide compound is at least one selected from the group consisting of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.
5. A method for preparing a hydrogenation catalyst, comprising the steps of preparing a mesoporous carbon carrier and introducing at least one group VIII metal element and at least one group VIB metal element into the mesoporous carbon carrier; the mesoporous carbon carrier contains carbon element, oxygen element, hydrogen element, sulfur element, nitrogen element and phosphorus element, wherein the content of the carbon element is 80-90 wt%, the content of the oxygen element is 2-6 wt%, the content of the hydrogen element is 0.1-1 wt%, the content of the sulfur element is 1-8 wt%, the content of the nitrogen element is 0.5-3 wt%, and the content of the phosphorus element is 0.5-10 wt%, based on the total weight of the mesoporous carbon carrier; the mesoporous carbon carrier preparation method comprises the following steps:
(1) Uniformly mixing a carbon carrier precursor, a phosphorus source and an adhesive to obtain a mixed material, wherein the carbon carrier precursor is asphalt powder and/or petroleum coke powder, the phosphorus source is a phosphorus-containing compound, and the phosphorus-containing compound comprises at least one of phosphoric acid, phosphate or a phosphorus-containing organic compound; (2) Carrying out heat treatment on the mixed material in an oxygen-containing atmosphere;
the phosphorus source is used in an amount of 0.5 to 8 parts by weight, preferably 1 to 6 parts by weight, based on phosphorus pentoxide, relative to 100 parts by weight of the asphalt powder and/or petroleum coke powder; the binder is used in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight.
6. The method according to claim 5, characterized in that the particle size of the bitumen powder and/or petroleum coke powder is 1-1000 μm, preferably 1-250 μm.
7. The method of claim 5, wherein the binder comprises at least one of a cellulose ether, a starch, or an enol polymer, preferably at least one of methylcellulose, hydroxyethyl methylcellulose, or hydroxypropyl methylcellulose.
8. The method according to claim 5, wherein the asphalt powder comprises petroleum asphalt powder and/or coal asphalt powder, wherein the asphalt powder contains polycyclic aromatic hydrocarbon, and the content of the polycyclic aromatic hydrocarbon is 70-100 wt%, preferably 85-100 wt%, based on the total weight of the asphalt powder.
9. The method according to any one of claims 5 to 8, wherein the conditions under which the mixed material is subjected to heat treatment under an oxygen-containing atmosphere include:
in an oxygen-containing atmosphere, the temperature of the mixed material is raised to 120-450 ℃ from room temperature according to the heating rate of 0.1-10 ℃/min, and the first heat treatment is carried out for 0.1-48 hours, so as to obtain an intermediate product;
and in an oxygen-containing atmosphere, the temperature of the intermediate product is increased to 700-1000 ℃ according to the heating rate of 0.1-10 ℃/min, and the second heat treatment is carried out for 0.1-12 hours, so as to obtain the mesoporous carbon carrier.
10. The method of claim 9, wherein the oxygen-containing atmosphere contains an oxygen-containing gas or a mixed gas of an oxygen-containing gas and an inert gas, wherein the oxygen-containing gas comprises at least one of oxygen, carbon dioxide, and carbon monoxide, and the inert gas comprises at least one of nitrogen, argon, and helium.
11. The method according to claim 5, further comprising the step of introducing an organic auxiliary agent selected from at least one of an organic acid and/or an ammonium salt thereof, an organic alcohol and a saccharide compound, simultaneously or sequentially with the active metal, on the mesoporous carbon support, the molar ratio of the organic auxiliary agent to the group VIII metal element being (0.3 to 2): 1; the organic acid is at least one of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid; the organic alcohol is at least one selected from glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol; the saccharide compound is at least one selected from the group consisting of triose, tetrose, pentose, D-glucose, D-galactose, D-mannose, D-fructose and sucrose.
12. Use of a hydrogenation catalyst according to any one of claims 1 to 4 or a catalyst obtainable by a process according to any one of claims 5 to 11 in the hydroprocessing of hydrocarbon oils.
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刘迎新;刘晓爽;曾茂;舒慧敏;楼炯涛;魏作君;: "硝基苯催化加氢合成对氨基苯酚的研究进展", 石油化工, no. 01, 15 January 2018 (2018-01-15) *

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