CN113856770B - Preparation method of sulfided hydrogenation catalyst, sulfided hydrogenation catalyst and application - Google Patents

Preparation method of sulfided hydrogenation catalyst, sulfided hydrogenation catalyst and application Download PDF

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CN113856770B
CN113856770B CN202010618961.4A CN202010618961A CN113856770B CN 113856770 B CN113856770 B CN 113856770B CN 202010618961 A CN202010618961 A CN 202010618961A CN 113856770 B CN113856770 B CN 113856770B
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catalyst
oil
temperature
content
carbon
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CN113856770A (en
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刘锋
夏国富
翟维明
晋超
褚阳
李会峰
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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    • 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
    • B01J37/20—Sulfiding
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a preparation method of a sulfur state hydrogenation catalyst, which comprises the steps of sequentially carrying out first heat treatment under the existence of a vulcanizing agent and impregnating oil, second heat treatment under the first reducing gas atmosphere, third heat treatment under the second reducing gas atmosphere and passivation treatment on an oxidation state catalyst; wherein the temperature of the three heat treatments is increased in sequence. Compared with the prior art, the preparation method provided by the invention is simpler and more effective, and the sulfided hydrogenation catalyst obtained by adopting the preparation method provided by the invention has better performance, and when the sulfided hydrogenation catalyst provided by the invention is applied, the startup time of a hydrogenation device can be greatly shortened, and the startup risk is reduced.

Description

Preparation method of sulfided hydrogenation catalyst, sulfided hydrogenation catalyst and application
Technical Field
The invention belongs to the field of hydrogenation catalysts, and particularly relates to a preparation method of a sulfided hydrogenation catalyst, a catalyst prepared by the method and application of the catalyst.
Background
Along with the heavy weight of crude oil resources, hydrocracking becomes a main technical means for producing clean gasoline and diesel oil and high-quality chemical raw materials. The catalyst used in the hydrogenation process takes VIB group metal such as molybdenum and/or tungsten, VIII group metal such as nickel and/or cobalt as an active component, and acidic materials such as alumina silica or molecular sieves and the like as a carrier. At present, in order to create economic benefits for completing production tasks after shutdown and overhaul of an oil refinery, immediate start-up at the fastest speed is often required, and the start-up process is required to be simple and rapid. Before the hydrogenation device is started, the hydrogenation catalyst has higher hydrogenation performance only by conventional preparation steps such as dipping, drying, roasting and the like, but also by sulfuration treatment to convert oxidized metal into sulfurated metal. The sulfuration process of the hydrogenation catalyst has the characteristics of high sulfuration temperature, high concentration of hydrogen sulfide, severe toxicity of the sulfuration agent, complex sulfuration process and the like. At present, most of the sulfuration of the hydrogenation catalyst is carried out in a reactor, one set of hydrogenation device is often required to carry out startup sulfuration every three years, and special equipment required in the sulfuration process is in an idle state in most of the operation time of the device, so that the investment of the device is additionally increased. The hydrogenation catalyst is vulcanized outside the reactor, so that the requirements of refineries on reducing the startup risk and saving the startup time can be met. Meanwhile, for a catalyst production plant, after the catalyst is prepared into an oxidation state by a production device, the catalyst is required to be sieved, packaged, transported to a vulcanizing device, and then packaged and filled for vulcanization, if the oxidation state preparation process and the vulcanization state preparation process of the catalyst can be combined together, the catalyst can be finished on one set of device, so that the production cost can be reduced, the total preparation time of the catalyst can be saved, the start-up time of an oil refinery can be saved, and good economic benefits can be created for the catalyst production plant and the oil refinery. The technical difficulty is how to complete the catalyst vulcanization process on an oxidation state catalyst preparation device.
Regarding the deactivation of sulfiding agents for hydrogenation catalysts, there have been many reports at home and abroad.
CN201010204326.8 discloses an external sulfuration method for catalyst, which comprises loading oxidized hydrogenation solid catalyst into sulfuration reactor, purging with inert gas, introducing pre-sulfuration gas, cooling, introducing oxygen-containing passivation gas, discharging the passivated catalyst from sulfuration reactor, bagging, sealing, transporting, storing, loading into hydrogenation reactor, purging with inert gas, heating, introducing activating sulfuration gas, and activating the sulfuration passivated catalyst. CN200880129246.1 discloses a method of incorporating sulfur in the pores of solid particles of a catalyst or adsorbent. CN1107701C discloses a method for vulcanizing a hydrotreating catalyst, wherein the hydrotreating catalyst is vulcanized by a method of first dry vulcanization and then wet vulcanization.
Disclosure of Invention
The invention aims at providing a preparation method of a sulfur state hydrogenation catalyst, the catalyst prepared by the method and application of the catalyst in hydrogenation reaction. In order to implement the present invention, the following description will be given of the specific contents of the present invention.
The invention provides a preparation method of a sulfur state hydrogenation catalyst, which comprises the following steps of sequentially carrying out the following treatment on the oxidation state catalyst:
(1) Performing first heat treatment on the oxidation state catalyst in the presence of a vulcanizing agent and impregnating oil under the inert gas atmosphere, wherein the treatment temperature is T1, and the treatment pressure is P1;
(2) Performing a second heat treatment on the catalyst obtained in the step (1) in a first reducing gas atmosphere, wherein the treatment temperature is T2, and the treatment pressure is P2;
(3) Performing third heat treatment on the catalyst obtained in the step (2) in a second reducing gas atmosphere, wherein the treatment temperature is T3, and the treatment pressure is P3;
(4) Passivating the catalyst obtained in the step (3) in a passivation gas atmosphere;
wherein T3> T2> T1.
The invention also provides the prepared sulfided hydrogenation catalyst and the application of the sulfided hydrogenation catalyst, wherein the catalyst is filled into a hydrogenation reactor and then directly introduced into raw oil for reaction; the reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours -1 Hydrogen oil volume ratio is 50-5000; the reaction conditions are preferably: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is 0.3-6 hours -1 The hydrogen-oil ratio is 50-1000.
Compared with the prior art, the preparation method of the sulfidic hydrogenation catalyst provided by the invention is simpler and more effective, and the sulfidic hydrogenation catalyst obtained by adopting the preparation method provided by the invention has better performance, and when the sulfidic hydrogenation catalyst provided by the invention is applied, the startup time of a hydrogenation device can be greatly shortened, and the startup risk is reduced.
Detailed Description
In order to better understand the present invention, the following will explain and explain the technical scheme of the present invention. It is first noted that endpoints of the ranges and any values disclosed in the specification are not limited to the precise range or value, and that the range or value is to be understood as encompassing values close to the range or value. 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 preparation method of the sulfided hydrogenation catalyst provided by the invention mainly comprises three heat treatment and one passivation processes. Wherein, the starting material is usually an oxidation state hydrogenation catalyst. The source of the oxidation state hydrogenation catalyst is not limited, and the oxidation state hydrogenation catalyst can be a commercial reagent or an oxidation state hydrogenation catalyst prepared according to the prior art. In general, the oxidation state hydrogenation catalyst comprises a support, at least one metal component selected from group VIII and at least one metal component selected from group VIB, and with or without an organic compound. Wherein the carrier is porous heat-resistant inorganic oxide commonly used as a catalyst carrier, preferably alumina, wherein the alumina can be one or more selected from gamma, eta, theta, delta and alpha, preferably gamma-alumina. The alumina has the specific surface and pore volume of conventional alumina, and the specific surface of preferential alumina is 150-350 m 2 Per gram, more preferably 180 to 320 meters 2 Preferably, the pore volume of the alumina is 0.4 to 1.1 ml/g, and more preferably, 0.5 to 0.9 ml/g. Can be commercially available or can be prepared by any method in the prior art. For example, it may be obtained by molding and calcining a mixture of one or more selected from alumina trihydrate, alumina monohydrate, and amorphous aluminum hydroxide. The aluminum oxide is formed by conventional methods, such as tabletting, rolling balls, extruding strips and the like. In the case of molding by conventional methods, the material to be molded (for example, a mixture of one or more of alumina trihydrate, alumina monohydrate and amorphous aluminum hydroxide) is introduced to ensure that molding proceeds smoothlyThe auxiliary agent is allowed, for example, when extruding the strip, a proper amount of extrusion aid and water can be introduced into the material to be formed, and then extrusion molding is performed. The type and amount of the extrusion aid can be conventional in the art, for example, the common extrusion aid can be one or more selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene glycol. When the carrier is formed alumina, the carrier may contain one or more auxiliary components selected from silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide and beryllium oxide, and the mass fraction of the auxiliary components is below 10 wt%, preferably 0.3-5 wt% based on the carrier. Further, when the carrier is formed alumina and one or more auxiliary components selected from the group consisting of silica, titania, magnesia, zirconia, thoria and beryllium oxide are contained or not contained, the carrier may further contain clay and/or molecular sieve, and the mass fraction of the clay and/or molecular sieve is 35% or less by weight, preferably 1 to 20% by weight, based on the carrier. The active metal component of the catalyst is a conventional choice and may generally be selected from group VIII and group VIB metal components, for example, the group VIII metal component is selected from cobalt and/or nickel and the group VIB metal component is selected from molybdenum and/or tungsten. In the preparation process, the group VIII metal compound is selected from one or more of soluble compounds of the metals, for example, one or more of nitrate, acetate, carbonate, chloride and soluble complex of the metals. The group VIB metal compound is selected from one or more of soluble compounds of the metals, and can be one or more of molybdate, para-molybdate, tungstate, metatungstate and ethyl metatungstate. According to the method for preparing a sulfided hydrogenation catalyst provided by the present invention, the content of each component in the oxidation state catalyst as a starting material is not particularly limited, and may be adjusted accordingly according to the specific purpose. For example, the components are used in amounts such that the carrier content in the oxidation state catalyst is 40 to 95% by weight, the active metal content calculated as oxide is 5 to 40% by weight, and the organic content is 0 to 20% by weight.
According to the invention, the main purpose of step (1) is that the oxidation state catalyst adsorbs the carbon source of sulphide and carbon deposit and is initially sulphided under heating to form metal oxysulphide. The inventor of the present invention found in the research process that, once the sulfide is put into the catalyst, mixed with the catalyst and heat treated, the sulfide can have a better adsorption effect with the catalyst metal, hydrogen sulfide is not produced, and meanwhile, the immersion oil is put into the catalyst, so that under the inert gas heat treatment condition of the step (1), the catalyst is moderately carbon-deposited to protect the catalyst active phase. The carbon source and the vulcanizing medium are introduced simultaneously, so that the subsequent carbon deposition plays a good role in protecting the target active phase, the catalyst is prevented from being directly contacted with inferior raw oil to be quickly deactivated in the application process, and the initial activation stabilization is realized. The catalyst adsorbs sulfide, the metal oxide is converted into metal oxysulfide, the metal valence state is not changed, the adsorption reaction of sulfide is mainly used, for example, molybdenum exists in the form of molybdenum trioxide in the oxidized catalyst, and after the step (1), the molybdenum trioxide and the sulfide are subjected to the adsorption reaction to generate molybdenum oxysulfide. The sulfide may be a sulfiding agent capable of reacting with hydrogen to produce hydrogen sulfide, e.g., mercaptans, sulfides, disulfides, thiophenes, elemental sulfur, and the like. The oxidation state catalyst may be a calcined oxidation state catalyst or a complex oxidation state catalyst containing an organic substance, wherein the organic substance may be an organic substance commonly used for preparing complex catalysts, the organic substance is selected from organic carboxylic acids or ammonium salts thereof, and the organic carboxylic acids are selected from one or more of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid. In the specific implementation process, the oxidation state hydrogenation catalyst, the vulcanizing agent and the impregnating oil are placed in a reactor together, are fully and uniformly mixed in a stirring or rotating mode and the like, and are subjected to first heat treatment after the atmosphere is regulated to be inert gas.
According to the invention, the impregnating oil is an oil product which can be deposited with carbon during the vulcanization process. The oil product can be petroleum-based distillate oil, or bio-based distillate oil, such as diesel oil, wax oil, residual oil, vegetable oil, animal oil, etc., preferably bio-based distillate oil, and more preferably vegetable oil. The oil products are preferably catalytic gasoline, coker gasoline, catalytic diesel oil, coker diesel oil, slurry oil, residual oil, vegetable oil, animal oil and other oil products rich in olefin and/or aromatic hydrocarbon, and in the vulcanization process, the olefin and/or aromatic hydrocarbon is deposited with carbon under the conditions of high temperature and low hydrogen partial pressure. In order to better ensure the introduction of the carbon deposition precursor, the impregnating oil preferably contains unsaturated hydrocarbon, wherein the unsaturated hydrocarbon can be olefin, diene, alkyne, aromatic hydrocarbon and the like, and the content of the unsaturated hydrocarbon in the impregnating oil is more preferably not less than 10% by weight, or more preferably 20-50% by weight, and even more preferably contains a mixture of different types of carbon deposition precursor oil products.
According to the invention, the sulfiding agent may be any sulfur-containing compound, which may be hydrogen sulfide, or a substance which is convertible to hydrogen sulfide at high temperature, such as sulfur, thiol, sulfide, disulfide, polysulfide, thiophene, substituted thiophene, or the like.
According to the method provided by the invention, the heat treatment temperature in the first stage heat treatment reactor can be 20-400 ℃, the pressure is 0-10.0MPa, preferably the temperature is 100-350 ℃, the pressure is 0-5.0 MPa, further preferably the temperature is 150-300 ℃ and the pressure is 0-2 MPa.
The inert gas described in the present invention includes inert gases in the conventional sense such as helium, nitrogen, neon, argon, etc., and gases which do not participate in the reaction in the step, such as one or more of methane, ethane, propane, butane, carbon dioxide, and preferably nitrogen. Hydrogen is not needed in the step (1), so that no hydrogen sulfide is released in the process of the step (1), and corrosion of equipment is slowed down.
According to the invention, the main purpose of step (2) is to reduce the metal oxysulfide, which means to reduce the metal oxysulfide in a higher valence state to a metal sulfide in a lower valence state, for example, molybdenum disulfide is produced by reacting molybdenum monoxide with hydrogen to produce molybdenum disulfide and water, and the produced molybdenum disulfide is a high-activity hydrogenation active center. According to the invention, the first reducing gas in step (2) is preferably hydrogen, or a mixture of hydrogen and an inert gas and/or hydrogen sulfide; further preferably, hydrogen is slowly introduced during the heat treatment of step (2) at a rate that is based on substantially no hydrogen sulfide in the exhaust gas. Therefore, the metal oxysulfide gradually returns to form water, almost no hydrogen sulfide is generated in the reduction process, and all sulfur in the sulfide and metal are subjected to vulcanization reaction, so that on one hand, the utilization rate of the sulfur can be improved, and on the other hand, the emission can be reduced, and the corrosion of equipment can be slowed down.
According to the present invention, the heat treatment temperature of step (2) is required to be higher than that of step (1), preferably the heat treatment temperature of step (2) is 20 to 450 ℃, the pressure is 0 to 10.0MPa, more preferably the temperature is 100 to 400 ℃, the pressure is 0 to 5.0MPa, still more preferably the temperature is 150 to 350 ℃, and the pressure is 0 to 2MPa.
According to the invention, the purpose of the step (3) is to remove part of the organic carbide on the surface of the metal sulfide through hydrogenation in a reducing atmosphere, and the organic carbide reacts with hydrogen to generate micromolecular gaseous hydrocarbon, so that the micromolecular gaseous hydrocarbon is removed from the surface of the metal sulfide, part of the metal sulfide is exposed, the hydrogenation activity and the stability are high, and an active phase containing a small amount of carbon deposit can be directly contacted with poor raw materials in the application process. According to the present invention, the second reducing gas atmosphere in the step (3) is preferably hydrogen or a mixture of hydrogen and an inert gas; the second reducing gas atmosphere in the step (3) contains no hydrogen sulfide, and the surface of the catalyst is reduced in the presence of no hydrogen sulfide, so that the finally discharged gas contains no sulfide, only hydrogen, water and a small amount of organic matters are discharged, and pollution and equipment corrosion are reduced.
To further ensure that the heat treatment of step (3) is performed in the complete absence of hydrogen sulfide, a step of purging with an inert gas and/or hydrogen is preferably included between step (2) and step (3), said purging being such that the second reducing gas atmosphere is substantially free of hydrogen sulfide. By this operation it is further ensured that the off-gas discharged after the heat treatment of step (3) is substantially free of hydrogen sulphide.
According to the present invention, the heat treatment temperature of the step (3) is required to be higher than that of the step (2), preferably, the heat treatment temperature of the step (3) is 20 to 500 ℃, the pressure is 0 to 10.0MPa, more preferably, the temperature is 100 to 450 ℃, the pressure is 0 to 5.0MPa, still more preferably, the temperature is 150 to 400 ℃, and the pressure is 0 to 2MPa.
In a specific implementation, for the heat treatment temperature and pressure in each step, there may be more specific choices such as T1 of 100 to 300 ℃, preferably 150 to 250 ℃, P1 of 0 to 4.0MPa, preferably 0.2 to 2.0MPa; t2 is 200-400 ℃, preferably 250-350 ℃, P2 is 0.5-6.0MPa, preferably 1.0-3.0MPa; t3 is 280-480 ℃, preferably 300-400 ℃, P3 is 1-10.0MPa, preferably 1.5-5.0MPa. It is further preferred that the pressure of the three heat treatments is sequentially increased, i.e., P3> P2> P1.
The pressure described in the present invention is generally referred to as gauge pressure unless otherwise specified.
And (3) the passivation treatment in the step (4) is to selectively oxidize the metal sulfide exposed on the surface of the sulfidic catalyst, oxidize the metal sulfide into metal oxysulfide, and form a layer of protective film, so that oxygen is prevented from deeply oxidizing the metal sulfide in the catalyst, the passivation treatment is used for protecting the sulfidic catalyst, and the hydrogenation activity is prevented from being reduced due to long-term exposure to the air environment. The catalyst is passivated by using an oxygen-containing compound at a certain temperature, the oxidizing substance is preferably simple and easily available oxygen, other oxides such as water, ethanol and the like can be used, and the surface of the catalyst can be coated by using oil products with heavier fractions to isolate air, so that the catalyst can finish the processes of unloading, packaging, transporting and the like. The passivation is preferably carried out using oxygen, the inert gas preferably being nitrogen. According to the invention, the passivation treatment in step (4) is a conventional choice, for example, the conditions of the passivation treatment include: the oxidation temperature in the reactor is 20-100 ℃, the pressure is normal pressure-2.0 MPa, and the time is 1-10 hours; preferably, the oxidation temperature is 30-80 ℃ and the pressure is normal pressure-1.8 MPa; more preferably, the oxidation temperature is 40-60 ℃ and the pressure is normal pressureAbout 1.5MPa, and the volume space velocity of passivation gas is 100-3000 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The passivation gas atmosphere contains inert gas and oxygen-containing substances, wherein the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide, and the oxygen-containing substances are one or more of oxygen, water and ethanol; the oxygen-containing substance content in the passivation gas is 0.1-21 volume percent, and the nitrogen content is 79-99.9 volume percent; preferably, the oxygen-containing substance content is 0.3-15% by volume, and the inert gas content is 85-99.7% by volume; further preferably, the oxygen-containing substance content is 0.5 to 10% by volume, and the inert gas content is 90 to 99.5% by volume.
In order to provide the final as-sulfided hydrogenation catalyst with higher activity, the heat treatment of steps (1) - (3) may be controlled so that the final as-sulfided catalyst has a sulfiding degree of at least 30%, more preferably 40-95%, still more preferably 50-90%. In the present invention, the degree of sulfidation of the group VIII active metal A in the hydrogenation catalyst is defined as the percentage of the total amount of element A in the active phase A-B-S, and the degree of sulfidation of the group VIB active metal B in the hydrogenation catalyst is defined as B 4+ Percentage of the total amount of element B, active phases A-B-S and B 4+ The content of (B) can be calculated according to the analysis result of X-ray photoelectron spectroscopy, and is specifically described in Limei (X-ray photoelectron spectroscopy for researching the chemical state [ J ] of the active element in the hydrodesulfurization catalyst]Petroleum report: petroleum processing, 2011, 27 (4): 638-642). For example, for cobalt molybdenum catalysts, the degree of sulfidation of molybdenum is defined as Mo 4+ The degree of sulfidation of cobalt is defined as the percentage of elemental Co in Co-Mo-S over the total Co.
On the other hand, the inventors of the present invention have found through further studies that the carbon content in the final catalyst, particularly the ratio of the carbon content having a decomposition temperature of 350 to 450 ℃ to the total carbon content has a significant influence on the initial activity stability of the catalyst. Therefore, in order to improve the stability of the initial activity of the catalyst, the amount of the impregnating oil in the step (1) is such that the ratio of carbon to metal content in terms of element in the finally obtained sulfided hydrogenation catalyst is 0.01 to 1, preferably 0.03 to 0.5, more preferably 0.05 to 0.3. The treatments of steps (1) - (4) are such that the carbon content in the final sulfided catalyst is from 1.5% to 30% by weight, preferably from 2.0% to 20% by weight; the proportion of the carbon content having a decomposition temperature of 350 to 450 ℃ in the carbon to the total carbon content is not less than 50% by weight, preferably not less than 60% by weight, and more preferably 65 to 95% by weight.
In addition, the inventor of the invention also finds that the catalyst prepared by the method of the invention has better initial activity and initial activity stability and better oxidation stability.
The total carbon content mentioned in the present invention refers to carbon which can be converted into carbon dioxide to be separated from the catalyst when the catalyst is heated to 800 ℃ in an air atmosphere, and carbon with a decomposition temperature of 350 ℃ to 450 ℃ refers to carbon which can be converted into carbon dioxide to be separated from the catalyst when the catalyst is heated to 350 ℃ to 450 ℃ in an air atmosphere. Specific testing and computing methods are set forth in the following description and examples.
The sulfided hydrogenation catalyst of the invention can be hydrofining, hydrocracking, hydrotreating catalyst and the like, so that the catalyst can be prepared by adopting the method provided by the invention. For other applications, catalysts or other materials that sulfur oxidized metals to sulfided metals are desired, and the methods provided by the present invention may also be used.
The invention also provides the catalyst prepared by the method and the application of the catalyst in hydrogenation reaction, in particular to the application in hydrofining reaction with hydrodesulfurization reaction as the main purpose, comprising the steps of filling the catalyst into a hydrogenation reactor and then directly introducing raw oil for reaction. The hydrogenation reaction conditions are not particularly limited, and preferable reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours -1 Hydrogen oil volume ratio is 50-5000; the reaction conditions are further preferably: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is 0.3-6 hours -1 The hydrogen-oil ratio is 50-1000.
The present invention will be described in detail with reference to the following specific examples, which are not intended to limit the scope of the invention.
The oxidation state hydrogenation catalysts used in the following examples and comparative examples were prepared by the following steps, unless otherwise specified: preparation of NiMo/Al Using an Industrial alumina Carrier (strip shape with outer diameter of 1.3mm and length of 2-4mm in Changling catalyst Co., ltd.) 2 O 3 The catalyst is specifically as follows: 20.98 g of molybdenum trioxide, 5.87 g of phosphoric acid and 9.15 g of basic nickel carbonate are weighed to prepare an aqueous solution, 100 g of alumina carrier is impregnated, air is introduced to dry after the impregnation, the drying temperature is 160 ℃, and the catalyst is baked for 4 hours at 420 ℃ after the drying is finished, so that the oxidation state hydrogenation catalyst C0 is obtained.
The loading of the catalysts used in the following examples and comparative examples was carried out by the following steps, unless otherwise specified: 20ml of catalyst and 16-18 mesh porcelain balls are mixed and put into a reactor constant temperature area of a small-sized reactor hydrogenation test device for hydrogenation reaction. The hydrogenation reaction uses straight-run diesel oil containing 20% of catalytic diesel oil, the sulfur content of raw oil is 0.98%, the reaction temperature is 340 ℃, the reaction pressure is 6.4MPa, and the volume space velocity is 1.5h -1 Hydrogen oil volume ratio 300.
The invention adopts NETZSCH STA409 instrument to analyze the proportion of carbon content and decomposition temperature between 350 and 450 ℃ to the total carbon content, the temperature of the sample is raised to 800 ℃ under the air atmosphere, the temperature raising rate is 10 ℃/min, and a mass spectrometer is used for monitoring at the instrument gas outlet to obtain the CO in the sample decomposition tail gas 2 Curve of concentration as a function of temperature. For CO 2 Peak-splitting fitting is carried out on the curve, and the decomposition temperature of CO is between 350 and 450 DEG C 2 Peak area divided by total CO 2 The peak area is the ratio of carbon with the decomposition temperature of 350-450 ℃ to the total carbon.
The unsaturated hydrocarbon in the impregnating oil is subjected to mass spectrometry to determine the group composition, and the determination method refers to the method of SH0606-2019, wherein the mass percent of the saturated hydrocarbon is determined, and the mass percent of the unsaturated hydrocarbon is=100% -the mass percent of the saturated hydrocarbon.
Example 1
1000 g of catalyst C0 is weighed and added into a rotary kiln reactor, 79 g of elemental sulfur and 100 g of coker gasoline are then added, the unsaturated hydrocarbon content of the coker gasoline is 49 wt%, nitrogen is filled after the air is removed, the pressure in the reactor is controlled to be 1.0MPa, the temperature is raised to 200 ℃ for the first heat treatment, and the temperature is kept constant for 6 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 1.5MPa, raising the temperature to 290 ℃, and carrying out heat treatment for the second time at constant temperature for 4 hours; introducing hydrogen to the pressure of 2.0MPa for the first time, raising the temperature to 340 ℃, and carrying out heat treatment for the third time at constant temperature for 3 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 3%, controlling the volume concentration of nitrogen to be 97%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 4 hours under the pressure of 1.0 MPa. The resulting catalyst was designated C1.
Example 2
1000 g of catalyst C0 is weighed and poured into a rotary kiln reactor once, 117 g of dimethyl disulfide and 195 g of catalytic diesel oil are poured into the rotary kiln reactor, the unsaturated hydrocarbon content in the catalytic diesel oil is 45%, nitrogen is filled after the air is removed, the pressure in the reactor is controlled to be 0.8MPa, the temperature is raised to 160 ℃ for the first heat treatment, and the temperature is kept constant for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours for secondary heat treatment; introducing hydrogen to the pressure of 2.5MPa for the first time, raising the temperature to 360 ℃, and carrying out heat treatment for the third time at constant temperature for 2 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 5%, controlling the volume concentration of nitrogen to be 95%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 2h and the pressure of 0.8 MPa. The resulting catalyst was designated C2.
Example 3
Weighing 1000 g of catalyst C0, pouring the catalyst C0 into a rotary kiln reactor once, pouring 80 g of elemental sulfur and 180 g of corn oil, wherein the unsaturated hydrocarbon content in the corn oil is 50%, removing air, then charging nitrogen, controlling the pressure in the reactor to be 1.5MPa, heating to 250 ℃ for primary heat treatment, and keeping the temperature for 3 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 300 ℃, and performing constant temperature for 4 hours for secondary heat treatment; introducing hydrogen to the pressure of 3.0MPa for the first time, raising the temperature to 360 ℃, and carrying out heat treatment for the third time at constant temperature for 2 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 1%, controlling the volume concentration of nitrogen to be 99%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 8h under the pressure of 1.0 MPa. The resulting catalyst was designated C3.
Example 4
Weighing 1000 g of catalyst C0, pouring the catalyst C0 into a rotary kiln reactor once, removing air, filling nitrogen, adding 79 g of hydrogen sulfide and 195 g of catalytic diesel, controlling the unsaturated hydrocarbon content in the catalytic diesel to be 45%, controlling the pressure in the reactor to be 0.8MPa, heating to 230 ℃ for primary heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 320 ℃, and keeping the temperature for 8 hours for secondary heat treatment; introducing hydrogen to the pressure of 2.5MPa for the first time, raising the temperature to 400 ℃, and carrying out heat treatment for the third time at constant temperature for 2 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 1%, controlling the volume concentration of nitrogen to be 99%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 2h and the pressure of 0.8 MPa. The resulting catalyst was designated C4.
Comparative example 1
20mL of catalyst C0 and 16-18 mesh porcelain balls are mixed and filled into a reactor constant temperature area of a small reactor hydrogenation test device, and the catalyst is vulcanized by an in-reactor vulcanization method, wherein the vulcanization pressure is 6.4MPa, and the volume space velocity is 2.0h -1 The hydrogen-oil volume ratio is 300, the sulfuration temperature is 320 ℃, the sulfuration time is 8 hours, sulfuration is carried out by using sulfuration kerosene with the DMDS concentration of 2 percent, the catalyst is named as D1, and the catalyst activity is directly evaluated after sulfuration.
Comparative example 2
Mixing 20mL of catalyst C0 and 16-18 mesh porcelain balls, loading into a reactor constant temperature area of a small reactor hydrogenation test device, vulcanizing the catalyst by using an in-reactor vulcanization method, wherein the vulcanization pressure is 0.3MPa, the gas-catalyst volume ratio is 400, the vulcanization temperature is 320 ℃, the vulcanization time is 8H, and H is used 2 The sulfided gas with S concentration of 3% was sulfided, the catalyst was named D2, and the catalyst activity was directly evaluated after sulfiding.
Comparative example 3
Weighing 1000 g of catalyst C0, pouring the catalyst C0 into a rotary kiln reactor once, pouring 79 g of elemental sulfur and 100 g of coker gasoline, wherein the unsaturated hydrocarbon content in the coker gasoline is 49%, removing air from the coker gasoline, then charging nitrogen, controlling the pressure in the reactor to be 1.0MPa, heating to 200 ℃ for primary heat treatment, and keeping the temperature for 6 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 1.5MPa, raising the temperature to 290 ℃, and carrying out heat treatment for the second time at constant temperature for 4 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 3%, controlling the volume concentration of nitrogen to be 97%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 4 hours under the pressure of 1.0 MPa. The resulting catalyst was designated D3.
Comparative example 4
1000 g of catalyst C0 is weighed and poured into a rotary kiln reactor once, 117 g of dimethyl disulfide and 195 g of catalytic diesel oil are poured into the rotary kiln reactor, the unsaturated hydrocarbon content in the catalytic diesel oil is 45%, nitrogen is filled after the air is removed, the pressure in the reactor is controlled to be 0.8MPa, the temperature is raised to 160 ℃ for the first heat treatment, and the temperature is kept constant for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours for secondary heat treatment; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 5%, controlling the volume concentration of nitrogen to be 95%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 4 hours under the pressure of 1.0 MPa. The resulting catalyst was designated as D4.
Comparative example 5
1000 g of catalyst C0 is weighed and poured into a rotary kiln reactor once, 117 g of dimethyl disulfide and 195 g of catalytic diesel oil are poured into the rotary kiln reactor, the unsaturated hydrocarbon content in the catalytic diesel oil is 45%, nitrogen is filled after the air is removed, the pressure in the reactor is controlled to be 0.8MPa, the temperature is raised to 350 ℃ for the first heat treatment, and the temperature is kept constant for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, reducing the temperature to 290 ℃, and performing heat treatment for the second time at constant temperature for 8 hours; introducing hydrogen to the pressure of 2.5MPa for the first time, reducing the temperature to 230 ℃, and performing heat treatment for the third time at constant temperature for 8 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 5%, controlling the volume concentration of nitrogen to be 95%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 2h and the pressure of 0.8 MPa. The resulting catalyst was designated as D5.
Comparative example 6
1000 g of catalyst C0 is weighed, poured into a rotary kiln reactor once, 117 g of dimethyl disulfide is poured into the rotary kiln reactor, nitrogen is filled after the air is removed, the pressure in the reactor is controlled to be 0.8MPa, the temperature is raised to 160 ℃ for the first heat treatment, and the temperature is kept constant for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours for secondary heat treatment; introducing hydrogen to the pressure of 2.5MPa for the first time, raising the temperature to 360 ℃, and carrying out heat treatment for the third time at constant temperature for 2 hours; and reducing the temperature of the reactor after discharging tail gas, controlling the volume concentration of oxygen in the reactor to be 5%, controlling the volume concentration of nitrogen to be 95%, and carrying out passivation treatment at the reaction temperature of 30-70 ℃ and the constant temperature for 2h and the pressure of 0.8 MPa. The resulting catalyst was designated as D6.
TABLE 1 catalyst sulfiding degree and hydrodesulfurization catalytic Performance
As can be seen from the results in Table 1, compared with the prior art, the hydrogenation catalyst obtained by the vulcanization method provided by the invention has better hydrodesulfurization activity, the decomposition temperature of the catalyst is 350-450 ℃ and the carbon content of the catalyst is higher than the total carbon, and meanwhile, the content of hydrogen sulfide in the tail gas is 0, so that the environment-friendly requirement is met.

Claims (17)

1. A preparation method of a sulfur state hydrogenation catalyst comprises the following steps of sequentially carrying out the oxidation state catalyst:
(1) Performing first heat treatment on the oxidation state catalyst in the presence of a vulcanizing agent and impregnating oil under the inert gas atmosphere, wherein the treatment temperature is T1, and the treatment pressure is P1;
(2) Performing a second heat treatment on the catalyst obtained in the step (1) in a first reducing gas atmosphere, wherein the treatment temperature is T2, and the treatment pressure is P2;
(3) Performing third heat treatment on the catalyst obtained in the step (2) in a second reducing gas atmosphere, wherein the treatment temperature is T3, and the treatment pressure is P3;
(4) Passivating the catalyst obtained in the step (3) in a passivation gas atmosphere;
wherein T3> T2> T1; t1 is 100-300 ℃, P1 is 0-10.0MPa; t2 is 200-400 ℃, P2 is 0-6.0MPa; t3 is 280-480 ℃, P3 is 0-10.0MPa;
the oxidation state catalyst comprises a carrier and active metals supported on the carrier, wherein the active metals are at least one metal component selected from VIII groups and at least one metal component selected from VIB groups, and the carrier is heat-resistant inorganic oxide;
the impregnating oil is petroleum distillate oil and/or bio-based distillate oil, the petroleum distillate oil is one or more of gasoline, diesel oil and residual oil, or is oil obtained by any one treatment process of catalytic cracking, coking, coal liquefaction and coal carbonization, and the bio-based distillate oil is vegetable oil and/or animal oil; the content of unsaturated hydrocarbon in the impregnating oil is not less than 10 weight percent, and the content of the impregnating oil is such that the ratio of carbon to metal in terms of elements in the finally obtained vulcanized hydrogenation catalyst is 0.01-1; the unsaturated hydrocarbon is at least one type of unsaturated compound containing aromatic hydrocarbon, olefin, diene and alkyne;
the first reducing gas in the step (2) is hydrogen or a mixed gas of hydrogen and inert gas and/or hydrogen sulfide; the second reducing gas atmosphere in the step (3) is hydrogen or a mixed gas of hydrogen and inert gas;
the conditions of the passivation treatment in step (4) include: the temperature is room temperature-100 ℃, the pressure is normal pressure-10 MPa, the time is 1-10 hours, and the volume airspeed of the passivation gas is 100-3000 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The passivation gas atmosphere contains inert gas and oxygen-containing substances, wherein the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide, and the oxygen-containing substances are one or more of oxygen, water and ethanol; the content of oxygen-containing substances in the passivation gas is 0.1-10% by volume, and the content of inert gas is 90-99.9% by volume.
2. The process according to claim 1, wherein the group VIII metal component is selected from cobalt and/or nickel, the group VIB metal component is selected from molybdenum and/or tungsten, and the support is alumina; the content of the carrier is 40-95 wt% based on the total amount of the oxidation state catalyst, the content of the active metal calculated by oxide is 5-40 wt% and the content of the organic matter is 0-20 wt%.
3. The method of claim 1, wherein the support is gamma-alumina.
4. The method of claim 1, wherein the sulfiding agent is one or more selected from elemental sulfur, hydrogen sulfide, carbon disulfide, mercaptans, sulfides, polysulfides, thiophenic sulfides.
5. The method according to claim 1, wherein the unsaturated hydrocarbon content in the impregnating oil is 20-50 wt%, and the impregnating oil is used in an amount such that the ratio of carbon to metal content in terms of elements in the finally obtained sulfided hydrogenation catalyst is 0.03-0.5.
6. The method according to claim 5, wherein the impregnating oil is used in such an amount that the ratio of carbon to metal content in terms of elements in the finally obtained sulfided hydrogenation catalyst is 0.05 to 0.3.
7. The method of claim 1, wherein the steps (2) and (3) further comprise a step of purging with an inert gas and/or hydrogen gas, the purging leaving the second reducing gas atmosphere substantially free of hydrogen sulfide.
8. The method of claim 1, wherein T1 is 150-250 ℃ and P1 is 0.2-5.0MPa; t2 is 250-350 ℃, P2 is 1.0-3.0MPa; t3 is 300-400 ℃, P3 is 1.5-5.0MPa.
9. The process according to claim 1, wherein the heat treatment of steps (1) - (3) results in a final sulfided catalyst having a sulfidation degree of at least 30%.
10. The process according to claim 9, wherein the heat treatment of steps (1) - (3) is such that the final sulfided catalyst has a sulfidation degree of 40-95%.
11. The process according to claim 10, wherein the heat treatment of steps (1) - (3) results in a final sulfided catalyst having a sulfidation degree of 50-90%.
12. The method according to claim 1, wherein the treatments of steps (1) to (4) are such that the carbon content in the finally obtained sulfided catalyst is 1.5% to 30% by weight; the carbon content of the carbon with the decomposition temperature of 350-450 ℃ accounts for not less than 50 weight percent of the total carbon content.
13. The method according to claim 12, wherein the treatments of steps (1) to (4) are such that the carbon content in the finally obtained sulfided catalyst is 2.0% to 20% by weight; the carbon content of the carbon with the decomposition temperature of 350-450 ℃ accounts for not less than 60 weight percent of the total carbon content.
14. The method according to claim 13, wherein the treatments of steps (1) to (4) are such that the ratio of the carbon content of the carbon having a decomposition temperature of 350 ℃ to 450 ℃ to the total carbon content in the finally obtained sulfided catalyst is 65 to 95% by weight.
15. A sulfided hydrogenation catalyst prepared by the process of any one of claims 1-14.
16. The use of the sulfided hydrogenation catalyst of claim 15, comprising loading the catalyst into a hydrogenation reactor and then directly introducing feed oil for reaction; the reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours -1 The volume ratio of hydrogen to oil is 50-5000.
17. The use of claim 16, wherein the reaction conditions comprise: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is0.3 to 6 hours -1 The hydrogen-oil ratio is 50-1000.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101822985A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Pre-treatment method of nickel hydrogenation catalyst
CN111068794A (en) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 External presulfurization method of hydrogenation catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101822985A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Pre-treatment method of nickel hydrogenation catalyst
CN111068794A (en) * 2018-10-22 2020-04-28 中国石油化工股份有限公司 External presulfurization method of hydrogenation catalyst

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