CN112742426B - Hydrogenation catalyst ex-situ presulfurization method - Google Patents

Hydrogenation catalyst ex-situ presulfurization method Download PDF

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CN112742426B
CN112742426B CN201911039472.7A CN201911039472A CN112742426B CN 112742426 B CN112742426 B CN 112742426B CN 201911039472 A CN201911039472 A CN 201911039472A CN 112742426 B CN112742426 B CN 112742426B
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situ
catalyst
hydrogenation catalyst
oil
weight
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CN112742426A (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
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/08—Heat treatment
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses an ex-situ presulfurization method of a hydrogenation catalyst. The method comprises the following steps: (1) Uniformly mixing a vulcanizing agent and an oxidation-state hydrogenation catalyst; (2) carrying out heat treatment on the mixture obtained in the step (1); (3) adding a phosphorus-containing substance into the mixture obtained in the step (2); (4) And (4) carrying out hydrogen treatment on the material obtained in the step (3) in the presence of hydrogen to obtain the pre-vulcanized catalyst. The method improves the ex-situ presulfurization process of the catalyst, improves the activity of the catalyst, avoids 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

Hydrogenation catalyst ex-situ presulfurization method
Technical Field
The invention relates to a hydrogenation catalyst presulfurization method, in particular to an ex-situ presulfurization method of a 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, an ex-situ prevulcanization technique has recently been developed. The external prevulcanization technology mainly comprises two technologies, namely a sulfur-carrying type external prevulcanization technology and a complete type external prevulcanization 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, mixing a carrier and thiomolybdate, drying, adding an adhesive, extruding into strips, drying under the protection of inert gas, and roasting to prepare the sulfidation type hydrotreating catalyst.
CN101618330B discloses a preparation method of a sulfuration type catalyst, which is to load a metal sulfide precursor on a carrier by an impregnation method, add a third component, enable the metal sulfide precursor to react with the metal sulfide precursor in pores of the carrier, and uniformly deposit metal sulfides in the pores, thereby preparing the sulfuration 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 an ex-situ presulfurization treatment method for a 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 ex-situ presulfurization method of the hydrogenation catalyst comprises the following steps:
(1) Uniformly mixing a vulcanizing agent and an oxidation-state hydrogenation catalyst;
(2) Carrying out heat treatment on the mixture in the step (1);
(3) Adding a phosphorus-containing substance into the mixture obtained in the step (2);
(4) And (4) carrying out hydrogen treatment on the material obtained in the step (3) in the presence of hydrogen to obtain the pre-vulcanized catalyst.
In the method of the present invention, step (5) is preferably added after step (4), and step (5) is to load the catalyst obtained in step (4) with hydrocarbon oil 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 method of the present invention, the hydrogenation catalyst in step (1) may be at least one of a hydrofining catalyst, a hydrocracking catalyst, a hydro-upgrading catalyst, and a hydrotreating catalyst, 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 comprises a carrier and active metal, wherein the carrier is an inorganic refractory oxide, the carrier mainly comprises alumina, and the active metal component comprises one or more of W, mo, ni and Co. The hydrogenation catalyst can also comprise an auxiliary agent component, and the auxiliary agent is selected from one or more of Si, B, ti, zr and the like.
In the method of the present invention, the vulcanizing agent in step (1) 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. Can be a single substance or a mixture, and is preferably cheap elemental sulfur (namely sulfur). 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 amount of sulfiding agent used is generally 80% to 150%, preferably 85% to 120%, of the theoretical sulfur requirement of the hydrogenation catalyst in the oxidized state. The active metal component contained in the hydrogenation catalyst whose theoretical sulfur demand is oxidation state is completely converted into sulfide (Co) 9 S 8 、MoS 2 、Ni 3 S 2 、WS 2 ) The amount of sulfur is needed.
In the step (1), in order to uniformly mix the vulcanizing agent and the oxidation state hydrogenation catalyst, other proper amount of vulcanizing auxiliaries such as organic solvents and the like 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 amount of the vulcanization aid used is 0.1 to 30%, preferably 1 to 25%, by weight of the hydrogenation catalyst in the oxidized state.
In the method of the invention, the heat treatment temperature in the step (2) is 70-500 ℃, preferably 120-270 ℃, and the heat treatment time is 10-480 min, preferably 15-240 min.
In the method, in the step (3), the temperature of the mixture obtained by the heat treatment in the step (2) 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 hydrogenation catalyst in an oxidation state.
In the method of the present invention, the phosphorus-containing substance in step (3) 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 ester, adenosine triphosphate, and the like, and preferably one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium phosphate. The phosphorus-containing substance is used in an amount of 0.1 to 50%, preferably 0.4 to 50%, by weight of the hydrogenation catalyst in the oxidized state.
In step (4) of the method, the hydrogen treatment conditions are as follows: the temperature is 50 to 450 ℃, preferably 150 to 320 ℃, the hydrogen pressure is 0.2 to 5.0MPa, preferably 0.5 to 3.5MPa, and the treatment time is 10 to 240min, preferably 30 to 120min.
In step (5) of the method of the present invention, the loading amount of the hydrocarbon oil is 0.5 to 20%, preferably 2.0 to 10% of the weight of the hydrogenation catalyst in an oxidized state, the hydrocarbon oil is generally a hydrocarbon oil obtained in a 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 method of the present invention, one or more of organic acids, organic nitrogen and the like are introduced as modifiers before, after or simultaneously with step (5) as required for adjusting the properties of the catalyst. The loading amount of the modifier is 0.5-20% of the weight of the hydrogenation catalyst in an oxidation state, and 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.
When the method of the invention is adopted to carry out ex-situ presulfurization on the hydrogenation catalyst, the following advantages are obtained:
(1) Compared with the conventional sulfur-carrying catalyst, the start-up time of the catalyst is further reduced;
(2) According to the method, after the oxidation state catalyst is contacted with the vulcanizing agent for heat treatment, the phosphorus-containing substance is added, and then hydrogen treatment is carried out, so that the metal sulfur phosphide in a specific state is formed, the initial reaction temperature of start-up activation can be further increased, the start-up operation requirement of the hydrogenation reactor is met, the safety of the hydrogenation reactor is improved, and the better vulcanization degree and higher catalyst activity of the ex-situ presulfurized catalyst are promoted; 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 oxidation-state 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 procedure and effect of the process of the invention will be further illustrated below by selecting the prior art hydrogenation catalyst for the ex-situ presulfiding treatment, without limiting the scope of the invention, and the properties of the main materials and catalysts referred to in the examples and comparative examples are shown in tables 1 to 5.
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 composition of diesel hydrogenation catalyst in oxidation state
Catalyst type Hydrogenation of diesel oil
Trade mark FHUDS-8
Carrier Alumina oxide
Active metal component Mo、Ni
Active metal content in terms of oxide,% by mass 30.7
Table 2 composition and main properties of industrial soybean oil
Comprises the following components:
palmitic acid,% 7.5
Oleic acid, content of 28.5
Stearic acid% 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 3 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 4 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 (20 ℃ C.)/mm 2 ·s -1 1.916
Flash point (off)/deg.C 51
Freezing point/. Degree.C <-60
Smoke point/mm 25
Arene, v% 5.6
TABLE 5 Main Properties of straight-run 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.)/mm 2 ·s -1 8.321
Flash point/. Degree.C 125
Cetane index 51.7
Example 1
The diesel hydrogenation catalyst FHUDS-8 in the oxidation state in Table 1 (catalyst amount 100 g) is presulfurized outside the reactor.
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 102 percent of the theoretical sulfur demand of an oxidation-state diesel hydrogenation catalyst), a vulcanizing aid (a mixture of industrial soybean oil shown in a table 2 and kerosene shown in a table 4, the using amount of which is 25 percent of the weight of the oxidation-state diesel hydrogenation catalyst FHUDS-8); uniformly mixing the pre-vulcanized raw material with an oxidation-state diesel hydrogenation catalyst;
(2) Carrying out heat treatment on the mixed material in the step (1) at 140 ℃ for 1h;
(3) Reducing the temperature of the mixed material in the step (2) to 60 ℃, then adding a mixture of 1.9g of phosphoric acid (the dosage is 1.9 percent of the weight of an oxidation state diesel hydrogenation catalyst FHUDS-8) and 30mL of ethanol, and uniformly mixing;
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 3.5MPa at 315 ℃ for 1.5h;
(5) The intermediate material in the step (4) is loaded with straight-run diesel oil as shown in Table 5, the load is 3% of the weight of the diesel oil hydrogenation catalyst FHUDS-8 in an oxidation state, and then the mixture is treated at 120 ℃ for 2 hours to obtain the pre-vulcanized catalyst 1.
Example 2
The diesel hydrogenation catalyst FHUDS-8 in the oxidation state in Table 1 (catalyst amount 100 g) is presulfurized outside the reactor.
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 115 percent of the theoretical sulfur demand of an oxidation state diesel hydrogenation catalyst), a vulcanizing additive (a mixture of industrial rapeseed oil and diesel oil in a weight ratio of 0.5 to 2, and the dosage of which is 9 percent of the weight of the oxidation state diesel hydrogenation catalyst FHUDS-8) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an oxidation-state diesel hydrogenation catalyst;
(2) Carrying out heat treatment on the mixed material in the step (1) at 235 ℃ for 1.5h;
(3) Reducing the temperature of the mixed material in the step (2) to 60 ℃, then adding 15g of diammonium hydrogen phosphate (the dosage is 15% of the weight of an oxidation state diesel hydrogenation catalyst FHUDS-8), and uniformly mixing;
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 0.5MPa at the temperature of 185 ℃ for 4 hours;
(5) And (5) loading citric acid into the material obtained in the step (4), introducing the material containing 7% of citric acid by weight of the diesel hydrogenation catalyst FHUDS-8 in an oxidation state, and then treating at 120 ℃ for 2 hours to obtain the pre-vulcanized catalyst 2.
Example 3
Carrying out ex-situ presulfiding on the diesel hydrogenation catalyst FHUDS-8 in an oxidation state in the table 1 (the using amount of the catalyst is 100 g);
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 90 percent of the theoretical sulfur demand of the diesel hydrogenation catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and white oil in a weight ratio of 2 to 1, and the dosage of which is 25 percent of the weight of an oxidation state diesel hydrogenation catalyst FHUDS-8) to obtain a pre-vulcanized raw material; uniformly mixing a pre-vulcanized raw material with an oxidation-state diesel hydrogenation catalyst;
(2) Carrying out heat treatment on the mixed material in the step (1) at 180 ℃ for 3.5h;
(3) Reducing the temperature of the mixed material in the step (2) to 60 ℃, then adding 0.5g of ammonium phosphate (the dosage is 0.5 percent of the weight of an oxidation state diesel hydrogenation catalyst FHUDS-8), and uniformly mixing;
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 3.0MPa for 4h at 295 ℃;
(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 according to the weight of the diesel hydrogenation catalyst FHUDS-8 in an oxidation state, and treating at 120 ℃ for 3 hours to obtain a presulfurization catalyst 3.
Example 4
Carrying out ex-situ presulfurization on the diesel hydrogenation catalyst FUDS-8 in an oxidation state in the table 1 (the dosage of the catalyst is 100 g);
(1) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 120 percent of the theoretical sulfur demand of the diesel hydrogenation catalyst) and a vulcanizing aid (a mixture of industrial soybean oil and gasoline in a weight ratio of 2 to 1, the using amount of which is 9 percent of the weight of the diesel hydrogenation catalyst FHUDS-8) to obtain a pre-vulcanization raw material; uniformly mixing the pre-vulcanized raw material with an oxidation state diesel hydrogenation catalyst;
(2) Carrying out heat treatment on the mixed material in the step (1) at 150 ℃ for 0.5h;
(3) Reducing the temperature of the mixed material in the step (2) to 60 ℃, then adding 44g of ammonium dihydrogen phosphate (the dosage is 44 percent of the weight of an oxidation state diesel oil hydrogenation catalyst FHUDS-8), and uniformly mixing;
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 0.6MPa for 1h at the temperature of 180 ℃;
(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 spraying according to the weight of the diesel hydrogenation catalyst FHUDS-8, and then treating at 120 ℃ for 2 hours to obtain the pre-vulcanized catalyst 4.
Example 5
Carrying out ex-situ presulfiding on the diesel hydrogenation catalyst FHUDS-8 in an oxidation state in the table 1 (the using amount of the catalyst is 100 g);
(1) Uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 85 percent of the theoretical sulfur demand of an oxidation state diesel hydrogenation catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2 to 1, and the dosage of which is 9 percent of the weight of the oxidation state diesel hydrogenation catalyst FHUDS-8) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an oxidation state diesel hydrogenation catalyst;
(2) And (3) carrying out heat treatment on the mixed material in the step at 170 ℃ for 3h.
(3) Reducing the temperature of the mixed material in the step (2) to 60 ℃, then adding 19g of adenosine triphosphate (the dosage is 19 percent of the weight of an oxidation state diesel hydrogenation catalyst FHUDS-8), and uniformly mixing;
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 2.5MPa 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 according to the weight of the diesel hydrogenation catalyst FHUDS-8, and then treating at 120 ℃ for 2 hours to obtain a pre-vulcanized catalyst 5.
Comparative example 1
Catalyst A was presulfided according to the procedure for example 1, eliminating step (3).
Comparative example 2
Catalyst B was presulfided as in example 2, eliminating step (3).
Comparative example 3
Carrying out ex-situ presulfurization on the diesel hydrogenation catalyst FUDS-8 in an oxidation state in the table 1 (the dosage of the catalyst is 100 g);
(1) Uniformly mixing 15g of diammonium phosphate with an oxidation-state diesel hydrogenation catalyst FHUDS-8;
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 115 percent of the theoretical sulfur demand of an oxidation state diesel hydrogenation catalyst) and a vulcanizing additive (a mixture of industrial rapeseed oil and diesel with the weight ratio of 0.5 to 2, the using amount of which is 9 percent of the weight of the oxidation state diesel hydrogenation catalyst FHUDS-8) to obtain a pre-vulcanization raw material; uniformly mixing a pre-vulcanized raw material and the mixture obtained in the step (1);
(3) And (3) carrying out heat treatment on the mixed material in the step (2) at 235 ℃ for 1.5h.
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 0.5MPa at the temperature of 185 ℃ for 4 hours;
(5) And (3) loading citric acid into the material obtained in the step (4), introducing the material containing 7% of citric acid by weight of the diesel hydrogenation catalyst FHUDS-8, and then treating at 120 ℃ for 2 hours to obtain a pre-vulcanized catalyst C.
Comparative example 4
(1) In the preparation process of an oxidation state diesel hydrogenation catalyst FHUDS-8, diammonium hydrogen phosphate is added into an active metal impregnation solution, the catalyst loaded with active metals is impregnated and dried at 120 ℃ to obtain a hydrogenation catalyst to be presulfurized, and the phosphorus content in the catalyst is 3.6wt%;
(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 115 percent of the theoretical sulfur demand of the diesel hydrogenation catalyst), a vulcanizing aid (a mixture of industrial rapeseed oil and diesel, the weight ratio of which is 0.5, and the dosage of which is 9 percent of the weight of the catalyst obtained in the step (1)); uniformly mixing a pre-vulcanized raw material with 115g of the catalyst obtained in the step (1);
(3) And (3) carrying out heat treatment on the mixed material in the step (2) at 235 ℃ for 1.5h.
(4) Treating the material obtained in the step (3) in a hydrogen atmosphere at the hydrogen pressure of 0.5MPa at the temperature of 185 ℃ for 4 hours;
(5) And (5) loading citric acid into the material obtained in the step (4), introducing the material containing 7% of citric acid by weight of the oxidation state diesel oil hydrogenation catalyst FHUDS-8, and then treating at 120 ℃ for 2 hours to obtain a pre-vulcanized catalyst D.
Example 6
The catalysts obtained in examples 1 to 5 and the catalysts obtained in comparative examples 1 to 4 were subjected to evaluation tests. The relative activities of the ex-situ presulfided catalysts were compared primarily.
The relative activity evaluation conditions were: the 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, and the volume space velocity is 2.5h -1 The reaction temperature was 350 ℃. Based on the activity of the presulfided catalyst B (100).
TABLE 6 Primary Properties of the feedstocks
Item Data of
Density (20 ℃), kg/m 3 853.3
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 A B C D
Desulfurization rate of% 130 117 127 123 126 108 100 105 110
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 (24)

1. An ex-situ presulfurization method of a hydrogenation catalyst is characterized by comprising the following steps:
(1) Uniformly mixing a vulcanizing agent and an oxidation-state hydrogenation catalyst;
(2) Carrying out heat treatment on the mixture in the step (1);
(3) Adding a phosphorus-containing substance into the mixture obtained in the step (2);
(4) Carrying out hydrogen treatment on the material obtained in the step (3) in the presence of hydrogen to obtain a pre-vulcanized catalyst;
the hydrogenation catalyst in an oxidation state in the step (1) comprises a carrier and active metal, wherein the active metal component comprises one or more of W, mo, ni and Co;
the temperature of the heat treatment in the step (2) is 120-270 ℃, and the time of the heat treatment is 15-240 min;
in the step (3), the temperature of the mixture obtained by the heat treatment in the step (2) is controlled to be 20-70 ℃, and then a phosphorus-containing substance is added;
the dosage of the phosphorus-containing substance in the step (3) is 0.1-50% of the weight of the hydrogenation catalyst in an oxidation state.
2. The ex-situ prevulcanisation process according to claim 1, characterized in that step (4) is followed by the addition of step (5): and (4) loading the catalyst obtained in the step (4) with hydrocarbon oil to obtain the pre-vulcanized catalyst.
3. The ex-situ presulfurization method according to claim 1, wherein the vulcanizing agent in step (1) is one or more of elemental sulfur and/or a sulfur-containing compound.
4. The ex-situ presulfurization method according to claim 1 or 3, wherein the amount of the sulfidizing agent is 80 to 150% of the theoretical sulfur demand of the hydrogenation catalyst in an oxidized state.
5. The ex-situ presulfurization method according to claim 4, wherein the amount of the sulfidizing agent is 85% to 120% of the theoretical sulfur requirement of the hydrogenation catalyst in an oxidized state.
6. The ex-situ presulfurization method according to claim 1, wherein a vulcanization aid is added in step (1).
7. The ex-situ presulfurization method according to claim 6, wherein the vulcanization aid is one or more of hydrocarbon oil and organic carboxylic acid ester.
8. The ex-situ prevulcanization method according to claim 7, wherein said hydrocarbon oil is one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricant base oil, straight run and decompressed heavy distillate oil; the organic carboxylic ester is an organic carboxylic ester containing 6-60 carbon atoms.
9. The ex-situ presulfurization method according to claim 7, wherein the organic carboxylic acid ester is one or more of fatty acid glyceride, animal oil, rapeseed oil, peanut oil, soybean oil, and cottonseed oil.
10. The ex-situ presulfurization process according to claim 6, wherein the amount of the vulcanization aid is 0.1 to 30% by weight of the hydrogenation catalyst in an oxidized state.
11. The ex-situ presulfurization process according to claim 6, wherein the amount of the vulcanization aid is 1% to 25% by weight of the hydrogenation catalyst in an oxidized state.
12. The ex-situ presulfurization method according to claim 1, wherein the phosphorus-containing substance in step (3) is selected from one or more of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, phosphoric acid esters, phosphorus pentoxide, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphonic acid esters, adenosine triphosphate.
13. The ex-situ presulfurization method according to claim 1, wherein the phosphorus-containing substance in step (3) is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium phosphate.
14. The ex-situ presulfiding method of claim 1, wherein the phosphorus-containing material of step (3) is used in an amount of 0.4 to 50% by weight of the hydrogenation catalyst in an oxidized state.
15. The ex-situ presulfurization method according to claim 1, wherein in the step (3), the phosphorus-containing substance is added together with an auxiliary agent, and the auxiliary agent is at least one of an alcohol and a hydrocarbon oil.
16. The ex-situ presulfurization method according to claim 1, wherein in the step (4), the hydrogen treatment conditions are: the temperature is 50-450 ℃, the hydrogen pressure is 0.2-5.0 MPa, and the treatment time is 10-240 min.
17. The ex-situ presulfurization method according to claim 16, wherein in the step (4), the hydrogen treatment conditions are: the temperature is 150-320 ℃, the hydrogen pressure is 0.5-3.5 MPa, and the processing time is 30-120 min.
18. The ex-situ presulfiding method according to claim 2, wherein the loading of the hydrocarbon oil in step (5) is 0.5-20% by weight of the hydrogenation catalyst in an oxidized state.
19. The ex-situ presulfiding method of claim 18, wherein the hydrocarbon oil loading in step (5) is 2.0-10% by weight of the hydrogenation catalyst in an oxidized state.
20. The ex-situ presulfurization method according to claim 2 or 18, wherein the hydrocarbon oil is a hydrocarbon oil obtained in a petroleum processing process, and has an initial boiling point of 150 ℃ or higher and an end boiling point of 550 ℃ or lower.
21. The ex-situ prevulcanization method according to claim 20, wherein the hydrocarbon oil is obtained from petroleum processing and has an initial boiling point of 180 ℃ or higher.
22. The ex-situ presulfurization process according to claim 2, wherein one or more of an organic acid and an organic nitrogen is introduced as a modifier before, after, or simultaneously with step (5).
23. The ex-situ presulfiding method of claim 22, wherein modifier loading is 0.5% to 20% by weight of the hydrogenation catalyst in the oxidized state.
24. The ex-situ presulfiding method of claim 23, wherein the modifier loading is 2.0% to 10% by weight of the hydrogenation catalyst in an oxidized state.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101417246A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Processing method before using hydrogenation catalyst
CN102989492A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
CN102989491A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Heavy oil hydrogenation protection catalyst, preparation and applications thereof
CN102989493A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Heavy oil hydrotreating composite catalyst preparation method
CN105854872A (en) * 2016-05-03 2016-08-17 四川凯沃斯能源科技有限公司 Catalyst for hydrodeoxygenation of bio-oil and preparation method of catalyst
CN108067310A (en) * 2016-11-15 2018-05-25 中国石油化工股份有限公司 A kind of ex situ presulfiding method of big pore volume hydrogenation catalyst
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 (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101417246A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Processing method before using hydrogenation catalyst
CN102989492A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Supported composite sulfur phosphide hydrotreatment catalyst, preparation and applications thereof
CN102989491A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Heavy oil hydrogenation protection catalyst, preparation and applications thereof
CN102989493A (en) * 2011-09-15 2013-03-27 中国石油天然气股份有限公司 Heavy oil hydrotreating composite catalyst preparation method
CN105854872A (en) * 2016-05-03 2016-08-17 四川凯沃斯能源科技有限公司 Catalyst for hydrodeoxygenation of bio-oil and preparation method of catalyst
CN108067310A (en) * 2016-11-15 2018-05-25 中国石油化工股份有限公司 A kind of ex situ presulfiding method of big pore volume hydrogenation catalyst
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 (2)

* Cited by examiner, † Cited by third party
Title
磷对预硫化型NiMo/Al2O3催化剂加氢脱硫脱氮性能的影响;相春娥等;《燃料化学学报》;20110531;第39卷(第5期);360页摘要 *
过渡金属磷化物的加氢精制催化性能研究进展;孙福侠等;《石油学报(石油加工)》;20051230(第06期);4-14 *

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