CN112742428A - Preparation method of vulcanization type hydrogenation catalyst - Google Patents

Preparation method of vulcanization type hydrogenation catalyst Download PDF

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Publication number
CN112742428A
CN112742428A CN201911040397.6A CN201911040397A CN112742428A CN 112742428 A CN112742428 A CN 112742428A CN 201911040397 A CN201911040397 A CN 201911040397A CN 112742428 A CN112742428 A CN 112742428A
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hydrogenation catalyst
oil
catalyst
solution
acid
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CN112742428B (en
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高玉兰
方向晨
徐黎明
佟佳
杨涛
王继锋
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

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

Abstract

The invention discloses a preparation method of a vulcanization type hydrogenation catalyst. The method comprises the following steps: (l) Respectively mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying to obtain an intermediate hydrogenation catalyst; (2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1); (3) carrying out heat treatment on the mixture obtained in the step (2); (4) adding a phosphorus-containing substance to the mixture of step (3); (5) and (4) carrying out hydrogen treatment on the material obtained in the step (4) in the presence of hydrogen to obtain the vulcanization type hydrogenation catalyst. The method improves the ex-situ presulfurization process of the catalyst, improves the activity of the catalyst, can avoid the safety problem of hydrogen brittleness of the reactor caused by overhigh initial activity temperature of the catalyst, and also solves the safety problem of the storage, transportation and filling processes of the ex-situ presulfurization catalyst.

Description

Preparation method of vulcanization type hydrogenation catalyst
Technical Field
The invention relates to a preparation method of a hydrogenation catalyst, in particular to a preparation method of a vulcanization type hydrogenation catalyst.
Background
In recent years, the crude oil deterioration tendency is increasingly obvious, the requirement of each country for clean fuel is increasingly increased, the hydrogenation process is taken as one of the most effective means for producing the clean fuel, and the high-efficiency hydrogenation catalyst becomes the technical key of the hydrogenation process. The active metal of the conventional hydrogenation catalyst is in an oxidation state, and the material which really plays an active role in actual use is in a vulcanization state, so the material needs to be vulcanized in a reactor before use. The conventional catalyst is presulfurized in a reactor, special equipment is needed, the production cost is increased, the vulcanization process is easy to cause pollution, and the required start-up time is longer.
In view of this problem, in recent years, ex-situ prevulcanization techniques have been developed. The external presulfurization technology mainly comprises two technologies of sulfur-carrying type external presulfurization technology and complete type external presulfurization technology. In the application of the sulfur-carrying type ex-situ presulfurization technology, because of the hydrogen brittleness requirement of the material of the reactor, the initial reaction temperature of the ex-situ presulfurization catalyst needs to be increased, and the activation also needs to be carried out in a reaction device; after the catalyst is fully presulfurized by the full ex-situ presulfurization technology, the catalyst can generate violent oxidation reaction (or referred to as a reverse sulfuration reaction) in air or oxygen-containing atmosphere, and can generate spontaneous combustion or explosion and other violent reactions when the catalyst is serious, and the prepared fully ex-situ presulfurization catalyst has safety problems of spontaneous combustion or explosion and the like in the processes of storing, transporting and filling a reaction device if the catalyst is not passivated and protected. In order to ensure the safety of catalyst storage, transportation and filling, a passivation process needs to be added in the pre-vulcanization process, and the equipment requirement is high and the operation condition is harsh, so that the overall catalyst pre-vulcanization cost is higher.
CN103769169A discloses a preparation method of a sulfidation type hydrotreating catalyst, which comprises mixing a carrier and thiomolybdate, drying, adding an adhesive, extruding into strips, molding, drying under the protection of inert gas, and calcining to obtain the sulfidation type hydrotreating catalyst.
CN101618330B discloses a preparation method of a sulfidation type catalyst, which comprises loading a metal sulfide precursor on a carrier by an impregnation method, adding a third component, reacting the third component with the metal sulfide precursor in pores of the carrier, and uniformly depositing metal sulfides in the pores, thereby preparing the sulfidation type catalyst.
The prior in-vitro presulfurization technology is utilized for treatment, the vulcanization process is still not very ideal, and the activity of the catalyst is influenced. Therefore, the ex-situ presulfiding method needs further improvement to improve the catalyst activity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a vulcanized hydrogenation catalyst, and aims to improve the ex-situ presulfurization process of the catalyst and improve the activity of the catalyst. Another object of the present invention is to avoid the safety problem of reactor hydrogen embrittlement due to excessive initial catalyst activation temperature. It is a further object of the present invention to address the safety of the ex-situ presulfided catalyst storage, transport and loading process.
The preparation method of the vulcanization type hydrogenation catalyst comprises the following steps:
(l) Mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying after mixing each time to obtain an intermediate hydrogenation catalyst;
(2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1);
(3) carrying out heat treatment on the mixture obtained in the step (2);
(4) adding a phosphorus-containing substance to the mixture of step (3);
(5) and (4) carrying out hydrogen treatment on the material obtained in the step (4) in the presence of hydrogen to obtain the vulcanization type hydrogenation catalyst.
In the method of the present invention, step (6) is preferably added after step (5), and step (6) is to load hydrocarbon oil on the catalyst obtained by hydrogen treatment in step (5) to obtain a presulfurized catalyst. The loading mode of the hydrocarbon oil can be adding modes such as dipping, soaking, spray dipping, spraying and the like.
In the step (1), the hydrogenation catalyst carrier may be at least one of a hydrofining catalyst carrier, a hydrocracking catalyst carrier, a hydro-upgrading catalyst carrier and a hydrotreating catalyst carrier, and may be used for hydrogenation of light distillate oil (such as gasoline, kerosene and diesel oil), hydrogenation of heavy distillate oil (such as wax oil), and hydrogenation of heavy oil (such as residual oil). The hydrogenation catalyst carrier is an inorganic refractory oxide, and mainly comprises alumina. The hydrogenation catalyst support can be prepared by a conventional method in the field.
In the step (1), the hydrogenation catalyst carrier may further include an auxiliary component, wherein the auxiliary is one or more selected from Si, B, Ti, Zr, and the like.
In the step (1), the hydrogenation catalyst carrier is respectively mixed with a thiomolybdate solution and/or a thiotungstate solution and a nickel salt solution and/or a cobalt salt solution, wherein the hydrogenation catalyst carrier can be firstly mixed with a thiomolybdate solution and/or a thiotungstate solution, dried, then mixed with a nickel salt solution and/or a cobalt salt solution, and dried to obtain an intermediate hydrogenation catalyst; or the hydrogenation catalyst carrier is mixed with a nickel salt solution and/or a cobalt salt solution, dried, mixed with a thiomolybdate solution and/or a thiotungstate solution, and dried to obtain the intermediate hydrogenation catalyst.
In the step (1), the drying conditions of the hydrogenation catalyst carrier after being mixed with the thiomolybdate solution and/or the thiotungstate solution are as follows: drying for 1-6 h at 30-250 ℃; the drying conditions of the hydrogenation catalyst carrier after being mixed with the nickel salt solution and/or the cobalt salt solution are as follows: drying for 1-6 h at 50-130 ℃.
The thiomolybdate in the step (1) may be one or more of ammonium thiomolybdate, potassium thiomolybdate, sodium thiomolybdate and the like, and is preferably ammonium thiomolybdate. The thiomolybdate is preferably one or more of tetrathiomolybdate and alkyl substituted thiomolybdate. The thiotungstate can be one or more of ammonium thiotungstate, potassium thiotungstate, sodium thiotungstate and the like, and preferably is ammonium thiotungstate. The thiotungstate is preferably one or more of tetrathiotungstate and alkyl substituted thiotungstate. The nickel salt and/or cobalt salt is selected from one or more of nitrate, carbonate, basic carbonate, acetate and chloride.
The mass concentration of the thiomolybdate and/or thiotungstate solution in the step (1) is 0.5-50%, preferably 3-25%; the mass concentration of the nickel salt solution and/or the cobalt salt solution is 0.2-200%, preferably 1.5-8%.
The total mass content of hydrogenation active metals contained in the intermediate hydrogenation catalyst in the step (1) is 5-50 wt%. Wherein, Mo and/or W accounts for 10-30% of the total mass content of the intermediate hydrogenation catalyst, and Ni and/or Co accounts for 0.5-8% of the total mass content of the intermediate hydrogenation catalyst.
The vulcanizing agent in step (2) may be a sulfur-containing substance conventional in the art, and may be one or more of elemental sulfur and/or a sulfur-containing compound. Inexpensive elemental sulfur (i.e., sulfur) is preferred. The sulfur-containing compound may be at least one of an inorganic sulfur-containing compound and an organic sulfur-containing compound, the inorganic sulfur-containing compound may be at least one of carbon disulfide and ammonium sulfide, and the organic sulfur-containing compound may be at least one of a mono-sulfur compound and a multi-sulfur compound, such as one or more of dimethyl disulfide, tert-butyl polysulfide, tert-nonyl polysulfide, thiourea, SZ-54 (commercial product), thiols (such as n-butyl thiol, ethyl thiol), thiophenol, thioether, sulfolane, dimethyl sulfoxide, and the like. The dosage of the vulcanizing agent is generally 5 to 120 percent, preferably 5 to 50 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst. The theoretical sulfur demand of the intermediate hydrogenation catalyst is that the active metal components contained in the intermediate hydrogenation catalyst are completely converted into sulfides (Co)9S8、MoS2、Ni3S2、WS2) In the presence of sulfurAmount of the compound (A).
In the step (2), in order to mix the vulcanizing agent and the intermediate hydrogenation catalyst uniformly, other proper amount of vulcanizing assistant, such as organic solvent commonly used in the field, can be added. The vulcanizing assistant may be one or more of hydrocarbon oil and organic carboxylic ester, the hydrocarbon oil is one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil, straight run and reduced pressure heavy distillate oil, and the like, and the hydrocarbon oil obtained by secondary processing, such as the hydrocarbon oil obtained by catalytic cracking, thermal cracking and other processes, is preferred. The organic carboxylic ester can be organic carboxylic ester containing 6-60 carbon atoms, preferably one or more of fatty glyceride, animal oil, rapeseed oil, peanut oil, soybean oil, cottonseed oil, etc. The dosage of the vulcanization assistant is 0.1-30% of the weight of the intermediate hydrogenation catalyst, preferably 1-25%.
In the method, the heat treatment temperature in the step (3) is generally 70-500 ℃, preferably 120-270 ℃, and the heat treatment time is 10-480 min, preferably 15-240 min.
In the method, in the step (4), the temperature of the mixture obtained by the heat treatment in the step (3) is controlled to be 20-70 ℃, and then a phosphorus-containing substance is added. Wherein, the phosphorus-containing substance can be added independently, preferably together with the auxiliary agent, and the auxiliary agent is used for promoting the phosphorus-containing substance to be dispersed into the catalyst more uniformly. The auxiliary agent can be at least one of alcohols and hydrocarbon oil; the alcohol auxiliary agent is at least one of ethanol, propanol, glycol, glycerol and the like; the hydrocarbon oil is one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil and heavy distillate oil of straight run and pressure reduction. The addition amount of the auxiliary agent is 1-30% of the weight of the intermediate hydrogenation catalyst.
In the method of the present invention, the phosphorus-containing substance in step (4) may be a phosphorus-containing substance conventional in the art, and may be selected from phosphorus-containing compounds, specifically, one or more of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, phosphate esters, phosphorus pentoxide, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphonic acid, phosphinic acid, phosphonate esters, adenosine triphosphate, and the like, preferably one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium phosphate. The dosage of the phosphorus-containing substance is 0.1-50%, preferably 0.4-50% of the weight of the intermediate hydrogenation catalyst.
In step (5) of the method of the present invention, the hydrogen treatment conditions are: the temperature is 50-450 ℃, preferably 150-320 ℃, the hydrogen pressure is 0.2-5.0 MPa, preferably 0.5-3.5 MPa, and the treatment time is 10-240 min, preferably 30-120 min.
In the step (6) of the method, the loading amount of the hydrocarbon oil is 0.5-20%, preferably 2.0-10% of the weight of the intermediate hydrogenation catalyst in the step (1), the hydrocarbon oil is generally obtained in the petroleum processing process, the initial boiling point of the hydrocarbon oil is above 150 ℃, preferably above 180 ℃, and the final boiling point of the hydrocarbon oil is below 550 ℃.
In the process of the present invention, one or more of organic acids, organic nitrogen and the like may be introduced as a modifier before, after or simultaneously with step (6) as necessary for adjusting the properties of the catalyst. The loading amount of the modifier is 0.5-20% of the weight of the intermediate hydrogenation catalyst, preferably 2.0-10%. After introduction of organic acids, organic nitrogen, and the like, a suitable drying treatment may be employed. The organic acid and the organic nitrogen may be those conventionally used in the preparation of hydrogenation catalysts. For example, the organic acid may be at least one of citric acid, malic acid, lactic acid, sorbic acid, gluconic acid, tartaric acid, succinic acid, benzoic acid, acetic acid, and oxalic acid, and the organic nitrogen may be at least one of organic amine, amino acid, urea, amide, protein, aniline, and quaternary ammonium salt.
The preparation method of the vulcanization type hydrogenation catalyst has the following advantages:
(1) compared with the conventional sulfur-carrying catalyst, the start-up time of the catalyst is further reduced;
(2) the method firstly prepares the intermediate hydrogenation catalyst, then contacts with a vulcanizing agent for heat treatment, then adds a phosphorus-containing substance, and then carries out hydrogen treatment, thereby being beneficial to forming metal sulfur phosphide in a specific state, further improving the initial reaction temperature of start-up activation, meeting the requirements of start-up operation of a hydrogenation reactor, improving the safety of the hydrogenation reactor, and promoting better vulcanization degree and higher catalyst activity of the ex-situ presulfurization catalyst; in the vulcanization process, the phosphorus-containing substance is added after the heat treatment, so that the original pore structure of the catalyst is prevented from being damaged in the preparation process of the intermediate catalyst, and the reaction activity of the catalyst is further influenced.
(3) The safety problems of the ex-situ prevulcanization treatment process and the storage, transportation and filling processes of ex-situ prevulcanization products are solved.
Detailed Description
The following is a selection of the prior art hydrogenation catalyst for the ex-situ presulfiding treatment to further illustrate the process and effect of the method of the present invention, but not to limit the scope of the invention, and the main material properties referred to in the examples are as follows. The properties of the main feeds and catalysts referred to in the examples and comparative examples are shown in tables 1 to 4.
In the present invention, the unspecified percentages are mass fractions unless the skilled person considers that they are not in accordance with the common general knowledge in the art.
Table 1 main properties of industrial soybean oil
Consists of the following components:
palmitic acid,% of 7.5
Oleic acid, content of 28.5
Stearic acid, based on 4.1
Linoleic acid% 57.9
Linolenic acid content% 2.0
Acid value (KOH) mg. g-1 4.0
Water and volatile matter% 0.20
Insoluble impurities,% of 0.10
TABLE 2 Main Properties of gasoline
Item Gasoline (gasoline)
Density (20 ℃ C.)/g-cm-3 0.7363
Distillation range/. degree.C
IBP/10% 28/57
30%/50% 95/136
70%/90% 169/207
95%/EBP 221/229
TABLE 3 essential Properties of kerosene
Item Kerosene oil
Density (20 ℃ C.)/g-cm-3 0.8092
Distillation range/. degree.C
IBP/10% 170/183
30%/50% 193/203
70%/90% 215/233
95%/EBP 240/251
Viscosity of the oil（20℃）/mm2·s-1 1.916
Flash point (off)/deg.C 51
Freezing point/. degree.C <-60
Smoke point/mm 25
Arene, v% 5.6
TABLE 4 Main Properties of Diesel
Item Straight-run diesel oil
Density (20 ℃ C.)/g-cm-3 0.8223
Distillation range/. degree.C
IBP/10% 263/278
30%/50% 288/293
70%/90% 305/322
95%/EBP 327/354
Viscosity (20 ℃ C.)/mm2·s-1 8.321
Flash point/. degree.C 125
Cetane index 51.7
Example 1
(1) 100g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (the concentration is 30wt percent) and 15mL of silica gel (containing 15wt percent of silicon) are uniformly mixed, extruded into strips, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. Preparing tetrathiomolybdate solution (containing 27% of molybdenum oxide), mixing with the silicon-containing alumina carrier, and drying at 115 ℃ for 3 h. Then mixing with prepared nickel nitrate solution (containing nickel oxide 8%), drying at 75 deg.C for 3.5h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 20 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst) and a vulcanizing assistant (a mixture of industrial soybean oil and diesel oil, the weight ratio of which is 2:1 and is shown in table 1 and 4, and the dosage of which is 25 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an intermediate hydrogenation catalyst;
(3) and (3) carrying out heat treatment on the mixed material in the step (2) at 140 ℃ for 1 h.
(4) Reducing the temperature of the mixed material in the step (3) to 60 ℃, then adding 16mL of phosphoric acid (the amount of phosphoric acid (the content is 85 percent) and 15mL of deionized water which are respectively 1.9 percent of the weight of the intermediate hydrogenation catalyst, uniformly mixing the phosphoric acid and the deionized water), mixing the mixture with 30mL of ethanol, and uniformly mixing;
(5) and (4) treating the intermediate material in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 1.0MPa for 3h at the temperature of 320 ℃.
(6) The intermediate material in the step (5) is loaded with straight-run diesel oil as shown in Table 4, the load is 5% of the weight of the intermediate hydrogenation catalyst in the step (1), and then the straight-run diesel oil is treated at 120 ℃ for 2h to obtain the pre-vulcanized catalyst 1.
Example 2
(1) 100g of pseudo-boehmite (commercial product or self-product), 5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (the concentration is 30wt percent) and 15mL of silica gel (containing 15wt percent of silicon) are uniformly mixed, extruded into strips and molded, and roasted for 3 hours at 500 ℃ to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 110 deg.C for 3h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 15 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial rapeseed oil and diesel oil in a weight ratio of 1: 2) to obtain a pre-vulcanized raw material, wherein the pre-vulcanized raw material is uniformly mixed with the intermediate hydrogenation catalyst;
(3) and (3) carrying out heat treatment on the mixed material in the step (2) at 245 ℃ for 3.5 h.
(4) And (3) reducing the temperature of the mixed material in the step (3) to 60 ℃, adding 35g of diammonium hydrogen phosphate (the dosage is 50% of the weight of the intermediate hydrogenation catalyst), and uniformly mixing.
(5) And (4) treating the material obtained in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 1.5MPa for 3h at the temperature of 180 ℃.
(6) And (3) loading citric acid into the material obtained in the step (5), introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and treating at 140 ℃ for 6 hours to obtain the pre-vulcanized catalyst 2.
Example 3
(1) 100g of pseudo-boehmite (commercial product or self-product) roasted at 600 ℃, 5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and formed, and the mixture is roasted at 500 ℃ for 3 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared cobalt nitrate solution (containing cobalt oxide 10%), drying at 100 deg.C for 2.5h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 15 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst) and a vulcanizing additive (a mixture of industrial rapeseed oil and diesel oil in a weight ratio of 1: 2) to obtain a pre-vulcanized raw material;
(3) and (3) carrying out heat treatment on the mixed material in the step (2) at 245 ℃ for 3.5 h.
(4) And (4) reducing the temperature of the mixed material obtained in the step (3) to 60 ℃, adding 25g of diammonium hydrogen phosphate (the dosage is 50% of the dosage of the intermediate hydrogenation catalyst, and adding 35mL of deionized water), and uniformly mixing.
(5) And (4) treating the material obtained in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 1.5MPa for 3h at the temperature of 180 ℃.
(6) And (3) loading citric acid into the material obtained in the step (5), introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and treating at 140 ℃ for 6 hours to obtain the pre-vulcanized catalyst 3.
Example 4
(1) 100g of pseudo-boehmite (commercial product or self-product) dried at 150 ℃, 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. Preparing ammonium thiotungstate solution (containing 30% of molybdenum oxide), mixing with the silicon-containing alumina carrier, and drying at 115 ℃ for 3 h. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 110 deg.C for 1h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 5 percent of the theoretical sulfur demand of the intermediate state hydrogenation catalyst) and a vulcanizing auxiliary agent (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, and the dosage of which is 9 percent of the weight of the intermediate state catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an intermediate hydrogenation catalyst;
(3) and (3) carrying out heat treatment on the mixed material in the step (2) at the temperature of 150 ℃ for 0.5 h.
(4) And (3) reducing the temperature of the mixed material in the step (3) to 50 ℃, adding 44g of ammonium dihydrogen phosphate (the dosage accounts for 44% of the dosage of the intermediate hydrogenation catalyst), and drying at 110 ℃ for 3 h.
(5) And (4) treating the material obtained in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 0.6MPa for 1h at the temperature of 180 ℃.
(6) And (3) loading citric acid and lubricating oil into the material obtained in the step (5), introducing the material containing 5% of citric acid and 7% of lubricating oil according to the weight of the intermediate state hydrogenation catalyst, and treating at 120 ℃ for 2h to obtain a pre-vulcanized catalyst 4.
Example 5
(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 110 deg.C for 2h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 50 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst) and a vulcanizing auxiliary agent (a mixture of industrial soybean oil and white oil in a weight ratio of 2:1, the dosage of which is 25 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with the intermediate hydrogenation catalyst;
(3) and (3) carrying out heat treatment on the mixed material in the step (2) at 180 ℃ for 3.5 h.
(4) And (3) reducing the temperature of the mixed material in the step (3) to 50 ℃, adding 0.5g (the dosage is 0.5 percent of the dosage of the catalyst) (adding 15ml of deionized water into phosphoric acid (the content is 85 percent) with the dosage being 1.9 percent of the dosage of the intermediate state hydrogenation catalyst), and uniformly mixing.
(5) And (4) treating the material obtained in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 3.0MPa for 4h at 295 ℃.
(6) And (3) loading citric acid and lubricating oil into the material obtained in the step (5), introducing the material containing 5% of citric acid and 7% of lubricating oil according to the weight of the intermediate hydrogenation catalyst, and treating at 120 ℃ for 3h to obtain the pre-vulcanized catalyst 5.
Example 6
(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 55 deg.C for 6h, and preparing intermediate hydrogenation catalyst.
(2) Uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 35 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an intermediate hydrogenation catalyst;
(3) and (3) carrying out heat treatment on the mixed material in the step at 170 ℃ for 3 h.
(4) Reducing the temperature of the mixed material in the step (3) to 40 ℃, then adding 19g of adenosine triphosphate (the dosage accounts for 19% of the dosage of the intermediate hydrogenation catalyst), and uniformly mixing;
(5) and (4) treating the material obtained in the step (4) in a hydrogen atmosphere at the hydrogen pressure of 4.5MPa for 2h at the temperature of 190 ℃.
(6) And (3) loading citric acid and lubricating oil into the material obtained in the step (5), introducing the material containing 5% of citric acid and 7% of lubricating oil according to the weight of the intermediate hydrogenation catalyst, and treating at 120 ℃ for 2h to obtain a pre-vulcanized catalyst 6.
Comparative example 1
Comparative catalyst A was obtained by following the procedure of example 1, eliminating step (4).
Comparative example 2
Comparative catalyst B was obtained by following the procedure of example 2, eliminating step (4).
Comparative example 3
(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 55 deg.C for 6h, and preparing intermediate hydrogenation catalyst. Adding diammonium hydrogen phosphate into the intermediate hydrogenation catalyst to obtain a hydrogenation catalyst to be pre-vulcanized, wherein the phosphorus content in the hydrogenation catalyst to be pre-vulcanized is 6 wt%;
(2) uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 35 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing a presulfurized raw material with 115g of the hydrogenation catalyst to be presulfurized obtained in the step (1);
(3) carrying out heat treatment on the mixed material in the step (2) at 170 ℃ for 3 h;
(4) treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 4.5MPa for 2h at 190 ℃;
(5) and (3) loading citric acid and lubricating oil into the material obtained in the step (4), introducing the material containing 5% of citric acid and 7% of lubricating oil by weight of the intermediate hydrogenation catalyst, and treating at 120 ℃ for 2 hours to obtain a comparative catalyst C.
Comparative example 4
(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. And mixing the mixed solution with a prepared nickel nitrate solution containing 10 percent of nickel oxide), wherein the nickel nitrate solution contains diammonium hydrogen phosphate, and drying the mixture for 6 hours at the temperature of 55 ℃ to prepare the intermediate catalyst.
(2) Uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 35 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing a pre-vulcanized raw material and the intermediate catalyst obtained in the step (1);
(3) carrying out heat treatment on the mixed material in the step (2) at 170 ℃ for 3 h;
(4) treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 4.5MPa for 2h at 190 ℃;
(5) and (3) loading citric acid and lubricating oil into the material obtained in the step (4), introducing the material containing 5% of citric acid and 7% of lubricating oil by weight of the intermediate hydrogenation catalyst, and treating at 120 ℃ for 2 hours to obtain a comparative catalyst D.
Example 7
Evaluation tests were conducted on the catalysts obtained in examples 1 to 6 and the catalysts obtained in comparative examples 1 to 4. The relative activities after activation of different ex-situ presulfided catalysts were compared.
The relative activity evaluation conditions were: mixed diesel oil is used as raw oil (Table 6), the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 350:1, and the volume airspeed is 2.5h-1The reaction temperature was 345 ℃. Based on the activity of catalyst B (100).
TABLE 6 Primary Properties of the feedstocks
Item Data of
Density (20 ℃), kg/m3 853.3
Distillation range, deg.C
IBP/10% 217/277
30%/50% 296/309
70%/90% 327/356
95%/EBP 369/375
S，μg/g 15150
N，μg/g 118
Cetane number 59.0
Bromine number, gBr/100g 4.5
TABLE 7 comparison of hydrogenation activity of catalysts
Catalyst numbering 1 2 3 4 5 6 A B C D
Desulfurization rate% 130 116 127 123 126 124 108 100 103 106
From the above results, it can be seen that the ex-situ presulfurized catalyst obtained by the method of the present invention has higher catalytic performance.

Claims (19)

1. A preparation method of a vulcanization type hydrogenation catalyst is characterized by comprising the following steps:
(l) Respectively mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying to obtain an intermediate hydrogenation catalyst;
(2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1);
(3) carrying out heat treatment on the mixture obtained in the step (2);
(4) adding a phosphorus-containing substance to the mixture of step (3);
(5) and (4) carrying out hydrogen treatment on the material obtained in the step (4) in the presence of hydrogen to obtain the vulcanization type hydrogenation catalyst.
2. The method of claim 1, wherein step (5) is followed by the addition of step (6): and (4) loading the catalyst obtained in the step (6) with hydrocarbon oil, and carrying out vulcanization type hydrogenation catalyst.
3. The method according to claim 1, wherein in the step (1), the hydrogenation catalyst carrier is mixed with a thiomolybdate solution and/or a thiotungstate solution, dried, then mixed with a nickel salt solution and/or a cobalt salt solution, and then dried to obtain an intermediate hydrogenation catalyst; or mixing the hydrogenation catalyst carrier with a nickel salt solution and/or a cobalt salt solution, drying, mixing with a thiomolybdate solution and/or a thiotungstate solution, and drying to obtain the intermediate hydrogenation catalyst.
4. The process of claim 3, wherein in step (1), the hydrogenation catalyst support is dried after mixing with the thiomolybdate solution and/or the thiotungstate solution under the following conditions: drying for 1-6 h at 30-250 ℃; the drying conditions of the hydrogenation catalyst carrier after being mixed with the nickel salt solution and/or the cobalt salt solution are as follows: drying for 1-6 h at 50-130 ℃.
5. The process according to claim 1, characterized in that the mass concentration of the thiomolybdate and/or thiotungstate solution in step (1) is 0.5-50%, preferably 3-25%; the mass concentration of the nickel salt solution and/or the cobalt salt solution is 0.2-200%, preferably 1.5-8%.
6. The method according to claim 1, wherein the intermediate hydrogenation catalyst in step (1) contains hydrogenation active metals in a total mass content of 5wt% to 50 wt%; preferably, Mo and/or W accounts for 10-30% of the total mass content of the intermediate hydrogenation catalyst, and Ni and/or Co accounts for 0.5-8% of the total mass content of the intermediate hydrogenation catalyst.
7. The method according to claim 1, wherein the vulcanizing agent of step (2) is one or more of elemental sulfur and/or a sulfur-containing compound.
8. The method according to claim 1, wherein the sulfiding agent in step (2) is used in an amount of 5% to 120%, preferably 5% to 50%, of the theoretical sulfur requirement of the intermediate hydrogenation catalyst.
9. The method of claim 1, wherein a vulcanization aid is added in step (2); the vulcanizing assistant is preferably one or more of hydrocarbon oil and organic carboxylic ester; the hydrocarbon oil is preferably one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil, straight-run and reduced-pressure heavy distillate oil; the organic carboxylic acid ester is preferably an organic carboxylic acid ester containing 6 to 60 carbon atoms, and more preferably one or more of fatty glyceride, animal oil, rapeseed oil, peanut oil, soybean oil and cottonseed oil.
10. A process according to claim 9, characterised in that the vulcanisation aid is used in an amount of 0.1 to 30%, preferably 1 to 25% by weight of the intermediate hydrogenation catalyst.
11. The method according to claim 1, wherein the temperature of the heat treatment in the step (3) is 70-500 ℃, preferably 120-270 ℃, and the heat treatment time is 10-480 min, preferably 15-240 min.
12. The method according to claim 1, wherein in the step (4), the temperature of the mixture obtained by the heat treatment in the step (3) is controlled to be 20-70 ℃, and then the phosphorus-containing substance is added.
13. The method of claim 1, wherein the phosphorus-containing material of step (4) is selected from one or more of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, phosphate esters, phosphorus pentoxide, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphonic acid, phosphinic acid, phosphonate esters, adenosine triphosphate; preferably one or more of phosphoric acid, ammonium dihydrogen phosphate and ammonium phosphate.
14. The process according to claim 1, 12 or 13, characterized in that in step (4), the phosphorus-containing substance is used in an amount of 0.1% to 50%, preferably 0.4% to 50%, by weight of the intermediate hydrogenation catalyst.
15. The method of claim 1, wherein in step (4), the phosphorus-containing substance is added together with an auxiliary agent, and the auxiliary agent is at least one of alcohols and hydrocarbon oil.
16. The method according to claim 1, wherein in the step (5), the hydrogen treatment conditions are: the temperature is 50-450 ℃, preferably 150-320 ℃, the hydrogen pressure is 0.2-5.0 MPa, preferably 0.5-3.5 MPa, and the treatment time is 10-240 min, preferably 30-120 min.
17. The process according to claim 2, wherein in the step (6), the loading amount of the hydrocarbon oil is 0.5 to 20 percent, preferably 2.0 to 10 percent of the weight of the intermediate hydrogenation catalyst in the step (1).
18. The process of claim 1, wherein one or more of an organic acid, an organic nitrogen is introduced as a modifier before, after, or simultaneously with step (6).
19. The process according to claim 18, wherein the modifier loading is from 0.5% to 20%, preferably from 2.0% to 10% by weight of the intermediate hydrogenation catalyst.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107999092A (en) * 2016-10-31 2018-05-08 中国石油化工股份有限公司 A kind of sulfurized hydrogenation catalyst and preparation method thereof and gasoline hydrodesulfurizationmethod method
CN109908971A (en) * 2017-12-13 2019-06-21 中国石油化工股份有限公司 A kind of ex situ presulfiding method of hydrogenation catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107999092A (en) * 2016-10-31 2018-05-08 中国石油化工股份有限公司 A kind of sulfurized hydrogenation catalyst and preparation method thereof and gasoline hydrodesulfurizationmethod method
CN109908971A (en) * 2017-12-13 2019-06-21 中国石油化工股份有限公司 A kind of ex situ presulfiding method of hydrogenation catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
相春娥等: "磷对预硫化型NiMo/Al2O3催化剂加氢脱硫脱氮性能的影响", 《燃料化学学报》 *

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