CN114160168B - Sulfuration method of gasoline selective hydrogenation catalyst - Google Patents

Sulfuration method of gasoline selective hydrogenation catalyst Download PDF

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Publication number
CN114160168B
CN114160168B CN202010953556.8A CN202010953556A CN114160168B CN 114160168 B CN114160168 B CN 114160168B CN 202010953556 A CN202010953556 A CN 202010953556A CN 114160168 B CN114160168 B CN 114160168B
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temperature
vulcanization
catalyst
hydrogen
diene
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CN114160168A (en
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郭蓉
孙进
李扬
郑步梅
姚运海
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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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a vulcanization method of a gasoline selective hydrogenation catalyst, which comprises the following steps: (1) The gasoline selective hydrogenation catalyst bed in the reactor is subjected to airtight and wetting treatment; (2) Adjusting the temperature of the catalyst bed to 130-200 ℃, introducing a vulcanizing agent, and after hydrogen sulfide penetrates through the catalyst bed, raising the temperature of the catalyst bed to 200-260 ℃, and vulcanizing for 4-16 hours at constant temperature; (3) Introducing distillate oil containing 10-50 wt% of diene and/or alkyne for treatment; (4) Introducing vulcanizing agent again for vulcanization, wherein the vulcanization conditions are as follows: and (3) vulcanizing for 4 to 16 hours at the constant temperature of 300 to 400 ℃ and ending the vulcanization. The method has higher selectivity after the catalyst is vulcanized, and the selectivity is stably improved without a period of time.

Description

Sulfuration method of gasoline selective hydrogenation catalyst
Technical Field
The invention relates to a method for vulcanizing a gasoline selective hydrogenation catalyst.
Background
At present, strict standards are formulated for fuel oil quality by environmental protection regulations of various countries in the world, national V and VI standards are also formulated in China, and the sulfur content in gasoline is limited to be below 10 mug/g. Hydrodesulfurization (HDS) is a process conventionally used to treat FCC gasoline to produce low sulfur gasoline, and it is desirable to reduce olefin saturation as much as possible while hydrodesulfurizing to reduce octane number loss. The scientific research institutes such as the China petrochemical industry institute and the China petrochemical industry science institute develop corresponding process technologies and matched catalysts, the selectivity in the hydrogenation process is improved, and the olefin is prevented from being greatly hydrogenated and saturated while hydrodesulfurization is performed. However, the catalyst after vulcanization in the conventional vulcanization scheme has higher initial activity of olefin hydrogenation saturation, large octane number loss and needs to be stabilized for a period of time to reach good selectivity. How to further and rapidly increase the selectivity of the catalyst in the use process is still a problem to be solved.
CN201210409659.3 discloses a startup method of a gasoline selective hydrodesulfurization process. The method reduces the reaction pressure while changing the raw oil after presulfiding the catalyst, and improves the reaction pressure to normal production under the conventional condition after keeping the hydrodesulfurization reaction at a lower pressure for a period of time. The method can shorten the stabilization time of the selective hydrodesulfurization catalyst at the initial stage of startup, quickly improve the hydrodesulfurization selectivity of the catalyst and reduce the octane number loss of the hydrogenated product.
CN201310514534.1 discloses a method for improving selectivity of catalyst, adding catalyst selectivity regulation process between sulfuration process and normal production process, the catalyst selectivity regulation process is that the catalytic raw material is contacted with catalyst for 24-96 hr under the condition of catalytic reaction in the atmosphere of catalytic gas, the catalytic gas includes hydrogen and hydrogen sulfide, and the volume fraction of hydrogen is not less than 70%, and the volume fraction of hydrogen sulfide is 0.2% -5%, and the normal production process is that the gasoline raw material is contacted with catalyst under the condition of normal reaction in the atmosphere of hydrogen-rich gas to make hydrogenation reaction. By adopting the method provided by the invention, the selectivity of the catalyst can be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a vulcanization method of a gasoline selective hydrogenation catalyst, which has higher selectivity after the catalyst is vulcanized, and the selectivity is not required to be stably improved for a period of time.
The invention relates to a vulcanization method of a gasoline selective hydrogenation catalyst, which comprises the following steps:
(1) The gasoline selective hydrogenation catalyst bed in the reactor is subjected to airtight and wetting treatment;
(2) Adjusting the temperature of the catalyst bed to 130-200 ℃, introducing a vulcanizing agent, and after hydrogen sulfide penetrates through the catalyst bed, raising the temperature of the catalyst bed to 200-260 ℃, and vulcanizing for 4-16 hours at constant temperature;
(3) Introducing distillate oil containing 10-50 wt% of diene and/or alkyne for treatment;
(4) Introducing vulcanizing agent again for vulcanization, wherein the vulcanization conditions are as follows: and (3) vulcanizing for 4 to 16 hours at the constant temperature of 300 to 400 ℃ and ending the vulcanization.
In the method of the invention, the selective hydrodesulfurization catalyst for gasoline in the step (1) generally takes alumina or composite alumina containing auxiliaries such as silicon, titanium, zirconium, phosphorus, boron and the like as a carrier, takes VIB group and/or VIII group metals as active metal components, and can also contain one or more auxiliary components such as potassium, calcium, phosphorus, iron, zinc, copper, titanium, zirconium and the like. Group VIB is preferably Mo and/or W, most preferably Mo; the group VIII metal is preferably Co and/or Ni, most preferably Co. Based on the weight of the catalyst, the weight of the VIB group metal is 4-20 wt% based on oxide, the weight of the VIII group metal is 1-10 wt% based on oxide, and the content of the auxiliary agent is 0.2-15 wt%, preferably 0.5-10 wt% based on oxide. Such as FGH-21, FGH-31 catalysts developed by the pacifying petrochemical institute.
In the method of the present invention, the airtight and wetting treatment in step (1) is a process well known to those skilled in the art, and the general process is: drying the catalyst, airtight nitrogen, replacing hydrogen and airtight hydrogen, wherein the airtight is qualified; then introducing vulcanized oil into the reactor, and wetting the catalyst bed. Such vulcanized oils are well known to those of ordinary skill as straight run naphtha, straight run kerosene, hydrocracked naphtha or hydrocracked kerosene and the like.
In the process of the present invention, the vulcanizing agent described in step (2) is a vulcanizing agent commonly used in the art, such as H 2 S、CS 2 DMDS, thioether, etc. The total consumption of the vulcanizing agent is 105% -150% of the theoretical sulfur demand of the catalyst.
The vulcanization method according to the present invention, wherein the system pressure in steps (1), (2), (3), (4) is maintained at the normal operating pressure or the maximum pressure allowed by the system.
In the method of the invention, the distillate oil in the step (3) has a distillation range of 30-250 ℃ and can be one or more of straight-run naphtha, straight-run kerosene, hydrocracking naphtha or hydrocracking kerosene.
In the method of the invention, the diene and/or alkyne in the step (3) is diene and/or alkyne with a carbon number of 5-14 and a boiling point of not more than 250 ℃, such as one or more of isoprene, hexadiene, octadiene, alkadiene, phenylbutadiene, undecadiene, pentyne, hexyne, octyne, nonyne, methylnonyne, dodecene, isomers of the diene and alkyne, and the like.
In the method of the invention, the treatment conditions in the step (3) are as follows: the temperature is 110-170 ℃, the pressure is 0.5-2 MPa, and the liquid hourly space velocity is 3.0-10.0 h -1 The volume ratio of the hydrogen oil is 5-15: 1, 4-8 hours.
In the process of the present invention, the concentration of hydrogen sulfide during the sulfidation of steps (2) and (4) is controlled as is well known to those skilled in the art. In the constant temperature vulcanization process at 200-260 ℃ in the step (2), the concentration of hydrogen sulfide in the hydrogen is generally controlled to be 1000-20000 mu L/L; in the step (4), the concentration of hydrogen sulfide in hydrogen is generally controlled to be 5000-30000 mu L/L in the constant temperature vulcanization process at 300-400 ℃.
The end-of-vulcanization conditions described in step (4) of the process of the present invention are also well known to those skilled in the art. If the concentration of hydrogen sulfide in the circulating hydrogen reaches at least 10000 mu L/L, the water level of the high water diversion liquid is not increased.
In the method, after the vulcanization is finished, raw gasoline is directly changed into the raw gasoline, and the raw gasoline is adjusted to conventional reaction conditions for the selective hydrodesulfurization reaction, wherein the conventional reaction conditions are as follows: the temperature is 220-330 ℃, the reaction pressure is 0.5-4.0 MPa, the volume ratio of hydrogen to oil is 100:1-1000:1, and the liquid hourly space velocity is 2.0-10.0 h -1
For hydrodesulfurization catalysts, the group VIB and/or group VIII active metals have very low hydrodesulfurization activity in the oxidized state and need to be sulfided before having high desulfurization activity in the sulfided state. After the gasoline hydrogenation catalyst is vulcanized, two active sites of a desulfurization active center and an olefin hydrogenation saturation active center exist. If the selectivity of the catalyst is improved, the desulfurization active center of the catalyst needs to be enhanced, and the olefin hydrogenation saturation active center of the catalyst needs to be reduced. The method for reducing the initial activity of the hydrogenation saturation of the olefin of the catalyst through carbon deposition after vulcanization can also simultaneously accumulate carbon at the desulfurization active center so as to reduce the desulfurization activity.
The inventor of the invention finds through a great deal of experimental researches that the catalyst selectivity can be effectively improved by regulating and controlling the catalyst in the vulcanization process, after the catalyst is initially vulcanized under the condition of lower temperature, the active metal which is easy to be vulcanized on the carrier reacts to generate a vulcanization state, and part of metal which is firmly combined with the carrier still exists in an oxidation state. At the moment, under the conditions of certain pressure, temperature and lower hydrogen-oil ratio, distillate oil containing diene/alkyne is introduced as a regulating auxiliary agent, and a certain amount of carbon deposit is generated on the catalyst by regulating the diene/alkyne hydrogenation saturation process, so that most of olefin hydrogenation saturation active centers are eliminated; on the other hand, unvulcanized metal and the regulating and controlling auxiliary agent are combined to form a CoMoC phase, the interaction between the carrier and the metal is weakened, and meanwhile, the metal is isolated from each other as a space barrier, so that the active metal is further vulcanized completely in the subsequent high-temperature vulcanization process, and highly dispersed vulcanized metal is formed, so that the desulfurization active center position of the catalyst is enhanced, and the olefin hydrogenation saturation center position of the catalyst is reduced. Through the regulation and control of the whole vulcanization process, the selectivity of the catalyst is improved.
Detailed Description
The following examples further illustrate the aspects and effects of the present invention, but do not limit the invention.
The invention calculates the selectivity factor of the catalyst according to the following formula, and the selectivity factor is used for measuring the selectivity of the catalyst.
S＝log(S p /S f )/log(O p /O f )。
Wherein: s-a selectivity factor; s is S p -sulfur content of gasoline product; s is S f -sulfur content of gasoline feedstock; o (O) p -the olefin content of the gasoline product by volume; o (O) f -the olefin content by volume of the gasoline feedstock.
In the embodiment and the comparative example, an FCC gasoline hydrodesulfurization catalyst FGH-31 (produced by Fushun petrochemical industry institute, china petrochemical catalyst Fushun division). The catalyst takes alumina as a carrier, co-Mo metal as an active component, and the active metal of the catalyst is 14% in terms of oxide. The specific surface area of the catalyst is 230 m 2 Per gram, pore volume of 0.45. 0.45 cm 3 /g。
The properties of the vulcanized oil and the raw oil are shown in Table 1.
Table 1 properties of the vulcanized oil and the raw oil.
Comparative example 1
Conventional sulfiding conditions for conventional hydrogenation catalysts are employed. The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to 1.6Mpa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/H, the vulcanizing agent is injected when the temperature is raised to 140 ℃, the vulcanizing agent is DMDS, the temperature is raised to 195 ℃ at 20 ℃/H, the temperature is constant, and the catalyst is heated to H 2 And after the S gas penetrates through the bed layer, continuously heating to 220 ℃ at 20 ℃/h, keeping the temperature for 6h, and continuously heating to 340 ℃ at 20 ℃/h after the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Example 1
The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to 1.6MPa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/H, the vulcanizing agent is injected when the temperature is raised to 140 ℃, the vulcanizing agent is DMDS, the temperature is raised at 20 ℃/H to 195 ℃ and is constant, and the catalyst is heated until the temperature reaches H 2 S gas continues to rise at 20 ℃/h after penetrating the bed layerAnd (3) heating to 220 ℃, keeping the temperature for 6 hours, cooling to 125 ℃ at 15 ℃/h after the constant temperature is finished, and introducing straight-run gasoline added with 4% of isoprene, 6% of 1, 3-butadiene, 5% of 1-hexyne and 5%1-octyne, wherein the total weight of the straight-run gasoline is 20% of diene/alkyne, and the distillation range is 48-172 ℃. The process conditions are as follows: the pressure is 1.5MPa, and the liquid hourly space velocity is 8.0h -1 Hydrogen-to-oil ratio 13:1, keeping the temperature for 6 hours. After the regulation is finished, the temperature is increased to 340 ℃ at 20 ℃/h, and the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Example 2
The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to 1.6MPa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/H, the vulcanizing agent is injected when the temperature is raised to 140 ℃, the vulcanizing agent is DMDS, the temperature is raised at 20 ℃/H to 195 ℃ and is constant, and the catalyst is heated until the temperature reaches H 2 And (3) continuously heating the bed layer to 220 ℃ at 20 ℃/h after the S gas penetrates through the bed layer, keeping the temperature for 6h, cooling the bed layer to 150 ℃ at 15 ℃/h after the constant temperature is finished, and introducing straight-run gasoline added with 30% of diene/alkyne of 12% of 1, 5-hexadiene, 12% of 1, 7-octadiene and 6% of 7-methyl-1-nonyne, wherein the distillation range is 48-200 ℃. The process conditions are as follows: the pressure is 0.7MPa, and the liquid hourly space velocity is 4.0h -1 Hydrogen to oil ratio 10:1, keeping the temperature for 6 hours. After the regulation is finished, the temperature is increased to 340 ℃ at 20 ℃/h, and the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 273 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Example 3
The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to 1.6MPa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/H, the vulcanizing agent is injected when the temperature is raised to 140 ℃, the vulcanizing agent is DMDS, the temperature is raised at 20 ℃/H to 195 ℃ and is constant, and the catalyst is heated until the temperature reaches H 2 The temperature of S gas is continuously raised to 220 ℃ at 20 ℃/h after penetrating through the bed layer, the temperature is kept for 6h, the temperature is reduced to 165 ℃ at 15 ℃/h after the temperature is kept, 15% isoprene is added,5% of butadiene, 10% of 1-hexyne and 10% of 1-dodecene, and 40% of diene/alkyne in total, wherein the distillation range is 150-250 ℃. The process conditions are as follows: the pressure is 1.2MPa, and the liquid hourly space velocity is 6.0h -1 Hydrogen to oil ratio 7:1, keeping the temperature for 5 hours. After the regulation is finished, the temperature is increased to 340 ℃ at 20 ℃/h, and the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Comparative example 2
The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to be 1.6MPa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/h, and when the temperature is raised to 150 ℃, the straight-run gasoline added with 12% of 1, 5-hexadiene, 12% of 1, 7-octadiene and 6% of 7-methyl-1-nonyne, wherein the total amount of 30% of diene/alkyne is injected, and the distillation range is 48-200 ℃. The process conditions are as follows: the pressure is 0.7MPa, and the liquid hourly space velocity is 4.0h -1 Hydrogen-to-oil ratio 13:1, keeping the temperature for 6 hours. After the regulation is finished, the process conditions are regulated by pumping vulcanized oil and the injection of vulcanizing agent is started, wherein the vulcanizing agent is DMDS, the temperature is increased to 195 ℃ at 20 ℃/H, the temperature is constant, and the temperature is kept until H 2 And after the S gas penetrates through the bed layer, continuously heating to 220 ℃ at 20 ℃/h, keeping the temperature for 6h, heating to 340 ℃ at 20 ℃/h after the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Comparative example 3
Pumping into a vulcanized oil wetting bed layer, heating at 20 ℃/H, injecting a vulcanizing agent which is DMDS when the temperature rises to 140 ℃, heating at 20 ℃/H to 195 ℃ constantly, heating at 20 ℃/H to 220 ℃ continuously after H2S gas penetrates through the bed layer, keeping the temperature for 6H, heating at 20 ℃/H to 340 ℃ continuously after the temperature is kept constant, and keeping the temperature for 8H. After the constant temperature is finished, the temperature is reduced to 150 ℃ at 15 ℃/h, and straight-run gasoline with the total of 30% of diene/alkyne, which is added with 12% of 1, 5-hexadiene, 12% of 1, 7-octadiene and 6% of 7-methyl-1-nonyne, is introduced, wherein the distillation range is 48-200 ℃. Art stripThe piece is: the pressure is 0.7MPa, and the liquid hourly space velocity is 4.0h -1 Hydrogen-to-oil ratio 13:1, keeping the temperature for 6 hours. After the regulation and control are finished, switching the raw oil according to the operation, wherein the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Comparative example 4
The catalyst is filled into a small reactor, the air tightness is qualified, the hydrogen partial pressure is regulated to be 1.6MPa, the catalyst is pumped into a vulcanized oil wetting bed layer, the temperature is raised at 20 ℃/H, the vulcanizing agent is started to be injected when the temperature is raised to 140 ℃, the vulcanizing agent is DMDS, the temperature is raised to 195 ℃ constantly at 20 ℃/H, the temperature is continuously raised to 220 ℃ at 20 ℃/H after the H2S gas penetrates through the bed layer, the temperature is kept for 6H after the temperature is kept constant, the temperature is raised to 250 ℃ at 15 ℃/H after the temperature is kept constant, the straight-run gasoline with the total of 30% of diene/alkyne added with 12% of 1, 5-hexadiene, 12% of 1, 7-octadiene and 6% of 7-methyl-1-nonane is introduced, and the distillation range is 48-200 ℃. The process conditions are as follows: the pressure is 0.7MPa, and the liquid hourly space velocity is 4.0h -1 Hydrogen-to-oil ratio 13:1, keeping the temperature for 6 hours. After the regulation is finished, the temperature is increased to 340 ℃ at 20 ℃/h, and the temperature is kept for 8h. After the constant temperature is finished, the raw oil is switched according to the operation, and the process conditions are as follows: the system pressure is 1.6MPa, and the liquid hourly space velocity is 3.0h -1 The hydrogen-oil ratio was 350, and after stable operation at 270 ℃ for 48 hours, the finished oil was sampled for analysis, and the catalyst activity was shown in table 2.
Table 2 refined oil properties.
As can be seen from Table 2, the catalyst selectivity can be effectively improved under the condition of producing low-sulfur gasoline by adopting the vulcanization method provided by the invention.

Claims (9)

1. A method for vulcanizing a gasoline selective hydrogenation catalyst, which is characterized by comprising the following steps: (1) The gasoline selective hydrogenation catalyst bed in the reactor is subjected to airtight and wetting treatment; (2) Adjusting the temperature of the catalyst bed layer to 130-200 ℃, and introducingAdding a vulcanizing agent, and after hydrogen sulfide penetrates through the catalyst bed, raising the temperature of the catalyst bed to 200-260 ℃, and vulcanizing for 4-16 hours at constant temperature; (3) Introducing distillate oil containing diene and/or alkyne for treatment; (4) introducing a vulcanizing agent again for vulcanization, and ending the vulcanization; the distillate oil in the step (3) has a distillation range of 30-250 ℃ and is selected from one or more of straight run naphtha, straight run kerosene, hydrocracking naphtha and hydrocracking kerosene; the content of the diene and/or alkyne in the step (3) is 10-50 wt%; the treatment conditions in the step (3) are as follows: the temperature is 110-170 ℃, the pressure is 0.5-2 MPa, and the liquid hourly space velocity is 3.0-10.0 h -1 The volume ratio of the hydrogen oil is 5-15: 1, 4-8 hours.
2. The vulcanization method according to claim 1, characterized in that: the airtight and wetting treatment process in the step (1) is as follows: drying the catalyst, airtight nitrogen, replacing hydrogen and airtight hydrogen, wherein the airtight is qualified; then introducing vulcanized oil into the reactor, and wetting a catalyst bed; the vulcanized oil is one or more of straight-run naphtha, straight-run kerosene, hydrocracking naphtha or hydrocracking kerosene.
3. The vulcanization method according to claim 1, characterized in that: the vulcanizing agent in the step (2) is H 2 S、CS 2 One or more of DMDS or thioether; the total consumption of the vulcanizing agent is 105% -150% of the theoretical sulfur demand of the catalyst.
4. The vulcanization method according to claim 1, characterized in that: the system pressure in steps (1), (2), (3), (4) is maintained at normal operating pressure or maximum pressure allowed by the system.
5. The vulcanization method according to claim 1, characterized in that: and (3) the diene and/or alkyne in the step (3) is diene and/or alkyne with a carbon number of 5-14 and a boiling point of not more than 250 ℃.
6. The vulcanization method according to claim 1, characterized in that: the diene and/or alkyne in the step (3) is isoprene, hexadiene, octadiene, sunflower diene, phenylbutadiene, undecadiene, pentyne, hexyne, octyne, nonyne, methylnonyne, dodecene and one or more of the isomers of the diene and alkyne.
7. The vulcanization method according to claim 1, characterized in that: in the step (2), in the constant temperature vulcanization process at 200-260 ℃, controlling the concentration of hydrogen sulfide in hydrogen to be 1000-20000 mu L/L; in the step (4), in the constant temperature vulcanization process at 300-400 ℃, the concentration of hydrogen sulfide in the hydrogen is controlled to be 5000-30000 mu L/L.
8. The vulcanization method according to claim 1, characterized in that: the vulcanization conditions are as follows: and vulcanizing for 4-16 hours at the constant temperature of 300-400 ℃.
9. The vulcanization method according to claim 1, characterized in that: after the vulcanization is finished, directly replacing raw gasoline, and adjusting to the reaction conditions to carry out selective hydrodesulfurization reaction, wherein the reaction conditions are as follows: the temperature is 220-330 ℃, the reaction pressure is 0.5-4.0 MPa, the volume ratio of hydrogen to oil is 100:1-1000:1, and the liquid hourly space velocity is 2.0-10.0 h -1 。
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