CN111117693B - Gasoline selective hydrodesulfurization method - Google Patents

Gasoline selective hydrodesulfurization method Download PDF

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CN111117693B
CN111117693B CN201811272595.0A CN201811272595A CN111117693B CN 111117693 B CN111117693 B CN 111117693B CN 201811272595 A CN201811272595 A CN 201811272595A CN 111117693 B CN111117693 B CN 111117693B
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catalyst
hydrodesulfurization
vulcanization
weight
carrier
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CN111117693A (en
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段为宇
郭蓉
周勇
姚运海
丁莉
杨成敏
孙进
刘丽
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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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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a selective gasoline additiveA method of hydrogen desulfurization comprising the steps of: two catalyst beds are arranged in a fixed bed reactor, a first catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst A, a second catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst B along the material flow direction, and raw oil sequentially passes through the catalyst beds to react under the hydrodesulfurization reaction condition to obtain a product; MoS based on the weight of a vulcanized hydrogenation catalyst A2Is 1wt% or more and less than 11wt%, Co9S8The weight content of the compound is 0.1wt% -7 wt%; MoS based on the weight of a vulcanized hydrodesulfurization catalyst B211-20% by weight of Co9S8The weight content of the compound is 0.1wt% -7 wt%; the catalyst loading volume ratio of the first bed layer to the second bed layer is 2/8-8/2. The method can effectively improve the activity and selectivity of the gasoline hydrodesulfurization reaction, and is suitable for industrial application.

Description

Gasoline selective hydrodesulfurization method
Technical Field
The invention relates to a gasoline selective hydrodesulfurization method.
Background
In recent years, in order to protect the environment, governments around the world strive to reduce the emission of harmful substances from the exhaust of internal combustion engines, and motor fuel quality specifications have become more stringent, particularly requiring a reduction in the sulfur content of motor gasoline. Combustion products SO of sulfur-containing compounds in gasolineXIs one of the main harmful substances of the automobile exhaust and is also one of the catalyst poisons of the automobile exhaust conversion device. Therefore, various countries in the world put forward the sulfur content in gasolineIncreasingly stringent limits are imposed.
It is well known that the sulfur content of straight run gasoline is primarily related to the sulfur content of crude oil, and that even though sulfur content is high, because of its low olefin content, there is no significant octane number loss when treated by conventional HDS processes. The sulfur and olefin contents of the FCC gasoline are high, and although the sulfur-containing compounds in the FCC gasoline can be effectively removed by adopting the traditional HDS method, the olefin with low branching degree in the FCC gasoline is very easy to be subjected to hydro-saturation to generate low-octane alkane, so that the traditional HDS method is inevitably accompanied with the sharp reduction of octane number along with the reduction of the sulfur content of the FCC gasoline.
CN102049271A discloses a gasoline selective hydrodesulfurization catalyst and a two-stage selective hydrodesulfurization process. The catalyst adopts alumina modified by titanium oxide and/or zirconium oxide as a carrier, P and K as auxiliary components, and Co and Mo as active metal components, although the hydrodesulfurization selectivity of gasoline is improved to a certain degree, the auxiliary components P and K have a limited inhibiting effect on the olefin saturation activity, so the hydrodesulfurization selectivity of the catalyst is still to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a gasoline selective hydrodesulfurization method. The method can effectively improve the activity and selectivity of the gasoline hydrodesulfurization reaction, and is suitable for industrial application.
The gasoline selective hydrodesulfurization method comprises the following steps: two catalyst beds are arranged in a fixed bed reactor, a first catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst A, a second catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst B along the material flow direction, and raw oil sequentially passes through the catalyst beds to react under the hydrodesulfurization reaction condition to obtain a product; MoS based on the weight of a vulcanized hydrogenation catalyst A2The weight content of (A) is more than 1wt% and less than 11wt%, preferably 2wt% to 9wt%, Co9S8The weight content of (B) is 0.1wt% -7 wt%, preferably 2wt% -6 wt%; MoS based on the weight of a vulcanized hydrodesulfurization catalyst B211-20% by weight of Co9S8Weight of (2)The content is 0.1wt% to 7wt%, preferably 2wt% to 6 wt%; the filling volume ratio of the catalyst of the first bed layer to the catalyst of the second bed layer is 2/8-8/2, preferably 3/7-8/2, and most preferably 4/6-8/2.
At least one of the sulfided hydrodesulfurization catalysts A, B is a sulfided hydrodesulfurization catalyst having the following properties, preferably sulfided hydrodesulfurization catalyst A, B: active phase MoS2The average length of the platelets is 4-14 nm, the preferred length is 7-11 nm, the average number of the platelets in a single stack layer is 1-12, the preferred number is 5.5-12, and the proportion of the stack layers with the number of layers larger than 5 is 10% -30% based on the total number of the stack layers; the pore volume of the catalyst is 0.3-1.3 mL/g, and the specific surface area is 150-400 m2/g。
The preparation method of the catalyst with the properties is as follows: (1) loading active metals Co and Mo on a carrier by adopting an impregnation method, and drying and roasting to obtain a semi-finished catalyst; (2) saturating and dipping the semi-finished catalyst obtained in the step (1) by using liquid olefin, and then performing heat treatment to deposit carbon; (3) and carrying out vulcanization treatment on the heat-treated catalyst to obtain the hydrodesulfurization catalyst.
Conventional equivalent saturated impregnation can be adopted in the step (1), and the concentration of the active metal component impregnation liquid is determined by the water absorption and the required catalyst composition (content).
The carrier in the step (1) is an inorganic refractory oxide, is selected from one or more of alumina, silica, zirconia, titania and magnesia, and is preferably alumina. The carrier can be modified by adding an auxiliary agent, and the modifying auxiliary agent can be K, Na, Mg, Si, P, Zr and Ti.
The drying conditions in the step (1) are as follows: drying for 1-5 hours at 100-120 ℃, wherein the roasting conditions are as follows: roasting at 400-550 ℃ for 1-5 hours.
The liquid olefin in the step (2) is normal or isomeric olefin and diolefin with 2-10 carbon atoms, and preferably hexadiene and/or n-heptene.
And (3) heating the heat treatment process in the step (2) at 50-250 ℃ for 1-8 h, heating to 250-300 ℃ for 1-72 h, and heating to 300-400 ℃ for 1-72 h for heat treatment.
And (3) adopting an in-situ or ex-situ vulcanization process for the vulcanization treatment, wherein the introduced vulcanizing agent accounts for 90-150% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, and the temperature is raised to 200-350 ℃ and is kept constant for 1-16 h.
The hydrogenation catalyst prepared by the method comprises hydrogenation active metal components of Co and Mo sulfide, carbon and a carrier, wherein the Mo sulfide is MoS based on the total weight of the catalyst2The content is 1.0-20.0%, preferably 1.0-18.0%, and Co sulfide is Co9S8The content is 0.1-7.0%, preferably 2-6.0%, the carbon content is 0.5-18.0%, and the carrier is inorganic refractory oxide, such as one or more of alumina, silicon oxide, zirconium oxide, titanium oxide or magnesium oxide, preferably alumina, and the content is 55-98%.
When a sulfided hydrodesulfurization catalyst of the above nature is selected, another may be a sulfided hydrodesulfurization catalyst conventional in the art, such as sulfided FGH-21, FGH-31, and the like.
In the method of the invention, the hydrodesulfurization reaction conditions are as follows: the reaction temperature is 230-320 ℃, preferably 250-300 ℃; the reaction pressure is 1.0 to 4.0MPa, preferably 1.6 to 3.2 MPa; the volume ratio of hydrogen to oil is 100-1000 Nm3/ m3More preferably 200 to 800Nm3/m3(ii) a The liquid hourly space velocity is 1.0-10.0 h-1More preferably 2.0 to 6.0 hours-1。
In the selective hydrogenation process of gasoline, how to inhibit the hydrogenation saturation of olefin while ensuring the hydrodesulfurization performance of the catalyst is always a contradiction which is difficult to balance. Through a large number of experiments, the catalyst obtained by a special carbon deposition mode is proved to have longer length of active phase plate crystals and more stacked layers after vulcanization, and the vulcanized catalyst with the structure has better hydrodesulfurization selectivity, so that the hydrodesulfurization activity is ensured, and the olefin saturation is better inhibited. The catalyst is applied to the two-stage hydrodesulfurization process, and the change of the content of active metal components of different beds is combined, so that the catalyst can keep high hydrodesulfurization activity and selectivity for a long time, the stable long-term operation of a gasoline selective hydrodesulfurization device is ensured, and the economy of the device is improved.
Drawings
FIG. 1 is a transmission electron micrograph of a catalyst of example 1 of the present invention.
FIG. 2 is a transmission electron micrograph of a comparative example 1 catalyst of the present invention.
Detailed Description
In the invention, the specific surface area and the pore volume of the catalyst are measured by a low-temperature liquid nitrogen adsorption method. The length of the platelets and the layer number of the stacks were determined using a field emission transmission electron microscope [ more than 350 MoS selected ]2Counting and arranging the average layer number, the average length and the proportion of wafers larger than 5 layers of the wafers, wherein the statistical formula is as follows:
Figure DEST_PATH_IMAGE001
and
Figure DEST_PATH_IMAGE002
wherein liRepresenting the wafer length, NiRepresents the number of i layers, aiRepresentative wafer liNumber of (a), (b)iNumber of representative layers NiThe number of (2). [ MEANS FOR solving PROBLEMS ] is provided. In the present invention, wt% means mass percentage.
The specific preparation process of the catalyst of the invention is as follows:
putting a carrier into a rolling pot, spraying Mo and Co ammonia solution with saturated water absorption of the carrier into the carrier in an atomization mode under a rotating condition, after the solution is sprayed, continuously rotating the carrier in the rolling pot for 10-60 minutes, then standing the carrier for 1-24 hours, drying the carrier for 1-5 hours at 100-120 ℃, raising the temperature to 400-550 ℃ at a heating rate of 150-250 ℃/hour, roasting the carrier for 1-5 hours to obtain a semi-finished catalyst, saturating the semi-finished catalyst with liquid olefin, heating the catalyst for 1-8 hours at 50-250 ℃, raising the temperature to 250-300 ℃, heating for 1-72 hours, raising the temperature to 300-400 ℃, heating for 1-72 hours, and carrying out heat treatment to obtain the oxidation state catalyst. Carrying out vulcanization treatment on the oxidation state catalyst by adopting an in-situ or out-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 90-150% of the theoretical sulfur demand of the catalyst, and the temperature is raised to 200-350 ℃ by adopting a programmed heating process in the vulcanization process and is kept constant for 1-16 h to obtain the finished product catalyst.
In the above preparation method, the concentration of the impregnation liquid is determined by the water absorption and the desired composition (content) of the catalyst.
The two-stage selective hydrodesulfurization using the catalyst of the present invention and the catalyst used therein are specifically illustrated by the following examples.
Example 1
Dissolving 11.1g of citric acid in 125mL of purified water, adding 8.2g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent (by weight) of ammonia water to 170mL, adding 14.5g of ammonium molybdate into the solution, adjusting the volume of the solution to 200mL by using 25 percent of ammonia water after dissolving, and sealing for storage. 200 g of carrier is placed in a rolling pot, spraying and soaking is carried out by using 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the carrier continues to rotate in the rolling pot for 30 minutes, then the carrier is placed for 18 hours, the carrier is dried for 3 hours at the temperature of 110 ℃, and then the carrier is heated to 500 ℃ at the heating rate of 200 ℃/hour and is roasted for 3 hours, thus obtaining the semi-finished catalyst A. And (3) placing the semi-finished catalyst A in 600mL of hexadiene solvent for soaking for 4h, then heating for 4h at 200 ℃, heating to 300 ℃ for 24h, and heating to 400 ℃ for 10h for heat treatment to obtain the oxidation state catalyst A. Carrying out vulcanization treatment on the oxidation state catalyst A by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so as to obtain the finished product catalyst A.
Example 2
Dissolving 20.9g of citric acid in 120mL of purified water, adding 15.5g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent by weight of ammonia water to 170mL, adding 29.5g of ammonium molybdate to the solution, adjusting the volume of the solution to 200mL by using 25 percent ammonia water after dissolving, and sealing for storage. 200 g of carrier is placed in a rolling pot, spraying and soaking is carried out by using 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the carrier continues to rotate in the rolling pot for 30 minutes, then the carrier is placed for 18 hours, the carrier is dried for 3 hours at the temperature of 110 ℃, and then the carrier is heated to 500 ℃ at the heating rate of 200 ℃/hour and is roasted for 3 hours, thus obtaining the semi-finished catalyst B. And (3) placing the semi-finished catalyst B in 600mL of hexadiene solvent for soaking for 4h, then heating for 4h at 200 ℃, heating to 300 ℃ for 24h, and heating to 400 ℃ for 10h for heat treatment to obtain the oxidation state catalyst B. And (3) carrying out vulcanization treatment on the oxidation state catalyst B by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that a finished product catalyst B is obtained.
Example 3
Dissolving 7.7g of citric acid in 150mL of purified water, adding 5.8g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent (by weight) of ammonia water to 170mL, adding 8.4g of ammonium molybdate into the solution, adjusting the volume of the solution to 200mL by using 25 percent of ammonia water after dissolving, and sealing for storage. 200 g of carrier is placed in a rolling pot, spraying and soaking is carried out by using 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the carrier continues to rotate in the rolling pot for 30 minutes, then the carrier is placed for 18 hours, the carrier is dried for 3 hours at the temperature of 110 ℃, and then the carrier is heated to 500 ℃ at the heating rate of 200 ℃/hour and is roasted for 3 hours, thus obtaining the semi-finished catalyst C. And (3) placing the semi-finished catalyst C in 600mL of hexadiene solvent for soaking for 4h, then heating for 4h at 200 ℃, heating to 300 ℃ for 24h, and heating to 400 ℃ for 10h for heat treatment to obtain the oxidation state catalyst C. And (3) carrying out vulcanization treatment on the oxidation state catalyst C by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst C is obtained.
Example 4
28.1g of citric acid is dissolved in 90mL of purified water, 20.9g of cobalt carbonate is added, the mixture is boiled and dissolved, after cooling, 25 percent by weight of ammonia water is added to 170mL, 45.6g of ammonium molybdate is added into the solution, after dissolution, the volume of the solution is adjusted to 200mL by 25 percent of ammonia water, and the solution is sealed and stored. 200 g of carrier is placed in a rolling pot, spraying and soaking is carried out by using 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the carrier continues to rotate in the rolling pot for 30 minutes, then the carrier is placed for 18 hours, the carrier is dried for 3 hours at the temperature of 110 ℃, and then the carrier is heated to 500 ℃ at the heating rate of 200 ℃/hour and is roasted for 3 hours, thus obtaining the semi-finished catalyst D. And (3) placing the semi-finished catalyst D in 600mL of hexadiene solvent for soaking for 4h, then heating for 4h at 200 ℃, heating to 300 ℃ for 24h, and heating to 400 ℃ for 10h for heat treatment to obtain the oxidation state catalyst D. And (3) carrying out vulcanization treatment on the oxidation state catalyst D by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst D is obtained.
Example 5
Dissolving 37.2g of citric acid in 40mL of purified water, adding 27.7g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent by weight of ammonia water to 170mL, adding 64.1g of ammonium molybdate to the solution, adjusting the volume of the solution to 200mL by using 25 percent ammonia water after dissolving, and sealing for storage. 200 g of carrier is placed in a rolling pot, spraying and soaking is carried out by using 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the carrier continues to rotate in the rolling pot for 30 minutes, then the carrier is placed for 18 hours, the carrier is dried for 3 hours at the temperature of 110 ℃, and then the carrier is heated to 500 ℃ at the heating rate of 200 ℃/hour and is roasted for 3 hours, thus obtaining the semi-finished catalyst E. And (3) placing the semi-finished catalyst E in 600mL of hexadiene solvent for soaking for 4h, then heating for 4h at 200 ℃, heating to 300 ℃ for 24h, and heating to 400 ℃ for 10h for heat treatment to obtain the oxidation state catalyst E. And (3) carrying out vulcanization treatment on the oxidation state catalyst E by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst E is obtained.
Comparative example 1
Dissolving 7.7g of citric acid in 150mL of purified water, adding 5.8g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent (by weight) of ammonia water to 170mL, adding 8.4g of ammonium molybdate into the solution, adjusting the volume of the solution to 200mL by using 25 percent of ammonia water after dissolving, and sealing for storage. 200 g of alumina carrier modified by carbon and silicon oxide according to a specific ratio is placed in a rolling pot, spraying and soaking are carried out by 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 18 hours, drying is carried out for 3 hours at 110 ℃, then the temperature is raised to 500 ℃ at the temperature raising speed of 200 ℃/hour, and the semi-finished catalyst F is prepared after roasting is carried out for 3 hours. And (3) carrying out vulcanization treatment on the semi-finished product catalyst F by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst F is obtained.
Comparative example 2
Dissolving 37.2g of citric acid in 40mL of purified water, adding 27.7g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent by weight of ammonia water to 170mL, adding 64.1g of ammonium molybdate to the solution, adjusting the volume of the solution to 200mL by using 25 percent ammonia water after dissolving, and sealing for storage. 200G of alumina carrier modified by carbon and silicon oxide according to a specific ratio is placed in a rolling pot, spraying and soaking are carried out by 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 18 hours, drying is carried out for 3 hours at 110 ℃, then the temperature is raised to 500 ℃ at the temperature raising speed of 200 ℃/hour, and the semi-finished catalyst G is obtained after roasting is carried out for 3 hours. And (3) carrying out vulcanization treatment on the semi-finished product catalyst G by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst G is obtained.
Comparative example 3
Dissolving 11.1g of citric acid in 125mL of purified water, adding 8.2g of cobalt carbonate, boiling for dissolving, cooling, adding 25 percent (by weight) of ammonia water to 170mL, adding 14.5g of ammonium molybdate into the solution, adjusting the volume of the solution to 200mL by using 25 percent of ammonia water after dissolving, and sealing for storage. 200 g of alumina carrier modified by carbon and silicon oxide according to a specific ratio is placed in a rolling pot, spraying and soaking are carried out by 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 18 hours, drying is carried out for 3 hours at 110 ℃, then the temperature is raised to 500 ℃ at the temperature raising speed of 200 ℃/hour, and the semi-finished catalyst H is prepared after roasting is carried out for 3 hours. And (3) carrying out vulcanization treatment on the semi-finished product catalyst H by adopting an in-situ vulcanization process, wherein the introduced amount of a vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst H is obtained.
Comparative example 4
28.1g of citric acid is dissolved in 90mL of purified water, 20.9g of cobalt carbonate is added, the mixture is boiled and dissolved, after cooling, 25 percent by weight of ammonia water is added to 170mL, 45.6g of ammonium molybdate is added into the solution, after dissolution, the volume of the solution is adjusted to 200mL by 25 percent of ammonia water, and the solution is sealed and stored. 200 g of alumina carrier modified by carbon and silicon oxide according to a specific ratio is placed in a rolling pot, spraying and soaking are carried out by 150mL of prepared molybdenum and cobalt ammonia solution, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 18 hours, drying is carried out for 3 hours at 110 ℃, then the temperature is raised to 500 ℃ at the temperature raising speed of 200 ℃/hour, and the semi-finished catalyst I is prepared after roasting is carried out for 3 hours. And (3) carrying out vulcanization treatment on the semi-finished product catalyst I by adopting an in-situ vulcanization process, wherein the amount of the introduced vulcanizing agent is 120% of the theoretical sulfur demand of the catalyst, and the vulcanization process adopts temperature programming, wherein the temperature is raised to 280 ℃ and is kept constant for 10 hours, so that the finished product catalyst I is obtained.
Example 6
The properties of catalysts A-I are shown in Table 1.
Carrying out selective hydrodesulfurization reaction on gasoline in a 200mL fixed bed small hydrogenation device, filling two catalyst bed layers, and carrying out reaction conditions as follows: the reaction pressure is 1.6MPa, and the liquid hourly volume space velocity is 3.0h-1Hydrogen/oil volume ratio of 300Nm3/m3The reaction temperature was 270 ℃, the sulfur content of the starting material was 664. mu.g/g, and the RON was 93.0. The specific loading ratio, the type of catalyst loaded, and the evaluation results of 600-hour operation are shown in Table 2.
TABLE 1 catalyst key Properties
Figure DEST_PATH_IMAGE003
TABLE 2 catalyst Activity and Selectivity
Figure DEST_PATH_IMAGE004
The results in Table 2 show that the selective hydrodesulfurization catalyst of the invention is adopted in two stages, and the selective hydrodesulfurization catalyst is adopted in one stage and the second stage, so that the octane number loss is small under the condition of the same desulfurization rate. After a certain running time, the catalyst of the invention has good activity and selectivity, and the selective hydrodesulfurization performance is more stable than that of a contrast catalyst.

Claims (9)

1. A gasoline selective hydrodesulfurization method is characterized in thatThe method comprises the following steps: two catalyst beds are arranged in a fixed bed reactor, a first catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst A, a second catalyst bed is filled with a vulcanization type hydrodesulfurization catalyst B along the material flow direction, and raw oil sequentially passes through the catalyst beds to react under the hydrodesulfurization reaction condition to obtain a product; MoS based on the weight of a vulcanized hydrogenation catalyst A2Is 1wt% or more and less than 11wt%, Co9S8The weight content of the compound is 0.1wt% -7 wt%; MoS based on the weight of a vulcanized hydrodesulfurization catalyst B211-20% by weight of Co9S8The weight content of the compound is 0.1wt% -7 wt%; the filling volume ratio of the first bed layer to the second bed layer is 2/8-8/2; at least one of the sulfided hydrodesulfurization catalysts A, B is a sulfided hydrodesulfurization catalyst having the following properties: active phase MoS2The average length of the platelets is 4-14 nm, the average number of the platelets in a single stack layer is 1-12, and the proportion of the stack layers with the number of layers larger than 5 is 10% -30% based on the total number of the stack layers; the preparation method of the vulcanization type hydrodesulfurization catalyst comprises the following steps: (1) loading active metals Co and Mo on a carrier by adopting an impregnation method, and drying and roasting to obtain a semi-finished catalyst; (2) saturating and dipping the semi-finished catalyst obtained in the step (1) by using liquid olefin, and then performing heat treatment to deposit carbon; (3) carrying out vulcanization treatment on the heat-treated catalyst to obtain a hydrodesulfurization catalyst; the carrier in the step (1) is inorganic refractory oxide.
2. The method of claim 1, wherein: at least one of the vulcanized hydrodesulfurization catalysts A, B is a vulcanized hydrodesulfurization catalyst with the following properties, the pore volume of the vulcanized hydrodesulfurization catalyst is 0.3-1.3 mL/g, and the specific surface area is 150-400 m2/g。
3. The method of claim 1, wherein: in the preparation method of the vulcanization type hydrodesulfurization catalyst, conventional equivalent saturated impregnation is adopted in the step (1), and the concentration of an active metal component impregnation liquid is determined by water absorption and the required catalyst composition.
4. The method of claim 1, wherein: in the preparation method of the vulcanization type hydrodesulfurization catalyst, the drying conditions in the step (1) are as follows: drying for 1-5 hours at 100-120 ℃, wherein the roasting conditions are as follows: roasting at 400-550 ℃ for 1-5 hours.
5. The method of claim 1, wherein: in the preparation method of the vulcanization type hydrodesulfurization catalyst, the liquid olefin in the step (2) is normal or isomeric olefin and diolefin with the carbon number of 2-10.
6. The method of claim 1, wherein: in the preparation method of the vulcanization type hydrodesulfurization catalyst, the heat treatment process in the step (2) is carried out for 1-8 h at 50-250 ℃, heated to 250-300 ℃ for 1-72 h, and then heated to 300-400 ℃ for 1-72 h for heat treatment.
7. The method of claim 1, wherein: in the preparation method of the vulcanization type hydrodesulfurization catalyst, the vulcanization treatment in the step (3) adopts an in-situ or ex-situ vulcanization process, the amount of the introduced vulcanizing agent is 90-150% of the theoretical sulfur demand of the catalyst, the vulcanization process adopts temperature programming, the temperature is raised to 200-350 ℃, and the temperature is kept for 1-16 hours.
8. The method of claim 1, wherein: the sulfuration type hydrodesulfurization catalyst comprises sulfides of hydrogenation active metal components Co and Mo, carbon and a carrier, wherein the total weight of the catalyst is taken as a reference, and the sulfide of the Mo is MoS2The content is 1.0-20.0%, and the sulfide of Co is Co9S8The content is 0.1% -7.0%, the carbon content is 0.5% -18.0%, and the carrier is an inorganic refractory oxide, and the content is 55% -98%.
9. The method of claim 1, wherein: the hydrodesulfurization reaction conditions are as follows: the reaction temperature is 230-320 ℃, andthe reaction pressure is 1.0-4.0 MPa, and the volume ratio of hydrogen to oil is 100-1000 Nm3/m3The liquid hourly space velocity is 1.0-10.0 h-1。
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CN114570391B (en) * 2020-12-02 2023-09-01 中国石油化工股份有限公司 Sulfuration type hydrodesulfurization catalyst and preparation method thereof
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CN102049269A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Selective hydrogenation catalyst for gasoline and preparation method thereof
CN102049271A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Gasoline selective hydrogenation catalyst and preparation method and application thereof

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CN102049270A (en) * 2009-10-27 2011-05-11 中国石油化工股份有限公司 Selective hydrogenation catalyst for gasoline and preparation method thereof
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