CN114437766B - Diesel oil hydrogenation start-up method using semi-vulcanization catalyst - Google Patents

Diesel oil hydrogenation start-up method using semi-vulcanization catalyst Download PDF

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CN114437766B
CN114437766B CN202011198551.5A CN202011198551A CN114437766B CN 114437766 B CN114437766 B CN 114437766B CN 202011198551 A CN202011198551 A CN 202011198551A CN 114437766 B CN114437766 B CN 114437766B
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catalyst
semi
vulcanization
hydrogenation
diesel
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CN114437766A (en
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杨成敏
刘丽
段为宇
郭蓉
周勇
李扬
姚运海
孙进
郑步梅
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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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/24—Starting-up hydrotreatment operations
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2400/04—Diesel oil

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

Abstract

A diesel oil hydroprocessing method using a semi-sulfided catalyst, comprising the following: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas-phase hydrogenation reaction, filling a semi-vulcanization catalyst in the hydrogenation reactor, circulating a gas-phase hydrogenation reaction product to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanization catalyst by utilizing hydrogen sulfide in the product until vulcanization is completed, and stopping circulating the gas-phase hydrogenation reaction product; the semi-sulfidation catalyst comprises a carrier and a hydrogenation active component, wherein the hydrogenation active component is a VIB group metal sulfide and a VIII group metal oxide. According to the invention, the semi-vulcanized catalyst is not subjected to an independent vulcanization process, but the materials of reaction products in the start-up stage are recycled, and the hydrogen sulfide in the semi-vulcanized catalyst is used for vulcanization treatment, so that effective utilization of bad substances is realized, the vulcanization process conditions are mild, and the reduction of the activity of the catalyst caused by overhigh local temperature in the vulcanization process is effectively inhibited.

Description

Diesel oil hydrogenation start-up method using semi-vulcanization catalyst
Technical Field
The invention relates to a diesel hydrogenation process, in particular to a diesel hydrogenation start-up method using a semi-vulcanization catalyst.
Background
The diesel hydrogenation catalyst is usually required to be vulcanized under certain conditions, generally wet vulcanization and dry vulcanization, and the catalyst is easy to have the problems of temperature runaway, hydrogen sulfide leakage and the like in the vulcanization process.
CN106669860a discloses a method for the sulfidation start-up of a hydrodesulfurization catalyst, comprising the following: (1) The reactor is filled with an oxidation state hydrodesulfurization catalyst with a second class of active centers; (2) The device is dried by a catalyst, airtight by nitrogen, airtight by hydrogen replacement and airtight by hydrogen; (3) Introducing vulcanized oil into the reactor, and wetting a catalyst bed; (4) adjusting the temperature of the catalyst bed, and changing into vulcanized oil I; after hydrogen sulfide penetrates through the catalyst bed, the temperature of the catalyst bed is increased to 180-240 ℃ and kept at the constant temperature for 4-16 hours; (5) Changing into vulcanized oil II, flushing the bed for 4-10 hours, and then raising the temperature of the catalyst bed to 250-330 ℃ and keeping the temperature for 4-16 hours; (6) After the vulcanization is finished, the technological conditions of the system are adjusted to the reaction conditions, and the raw oil is switched to perform normal operation. The catalyst is an oxidation state catalyst, the active component is a metal oxide of a VIB group and/or a VIII group, and the catalyst is required to be vulcanized and converted into metal sulfide with hydrodesulfurization activity. However, the group VIB metal oxide is harder to sulfide than the group VIII metal oxide, which results in the group VIII metal of the active metals being first sulfide and the group VIB metal being post sulfide, resulting in a reduction in the number of high active sites. In addition, the invention has complex vulcanization process, and the problems of temperature runaway, hydrogen sulfide leakage and the like are easy to occur in the vulcanization process.
CN105709859a discloses a sulfiding method for a fixed bed hydrogenation catalyst. The catalyst beds are vulcanized gradually from top to bottom by controlling circulating hydrogen carrying vulcanizing agent through adjusting control valves of cold hydrogen pipelines of the catalyst beds. The cold hydrogen boxes are arranged between the bed layers of the reactor, so that the cost of a refinery is increased, and meanwhile, the problems of temperature flying, hydrogen sulfide leakage and the like are easy to occur in the vulcanization method.
Disclosure of Invention
Aiming at the problems of complex vulcanization and reaction condition switching adjustment, poor vulcanization effect and early bed temperature flying of hydrogenation reaction in the prior art, the invention provides a diesel hydrogenation start-up method using a semi-vulcanization catalyst, wherein VIB group metal exists in a vulcanization state in the catalyst, sulfur in a reaction product is utilized to vulcanize oxidation state metal in the semi-vulcanization catalyst, unfriendly substances of the product are utilized, and the method has the effect of preventing the early bed temperature flying of start-up.
In order to solve the technical problems, the invention adopts the following technical scheme:
a diesel oil hydroprocessing method using a semi-sulfided catalyst, comprising the following: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas-phase hydrogenation reaction, filling a semi-vulcanization catalyst in the hydrogenation reactor, circulating a gas-phase hydrogenation reaction product to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanization catalyst by utilizing hydrogen sulfide in the product until vulcanization is completed, and stopping circulating the gas-phase hydrogenation reaction product;
the semi-sulfidation catalyst comprises a carrier and a hydrogenation active component, wherein the hydrogenation active component is a VIB group metal sulfide and a VIII group metal oxide.
Further, the VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni.
Further, the raw diesel is one or more of straight-run diesel, coked diesel and catalytic diesel.
Further, the vulcanization is completed under conditions that the sulfur content in the liquid phase product is less than 10ppm and the nitrogen content is less than 2.0ppm.
Further, the reaction conditions in the hydrogenation reactor at the start-up stage are as follows: the reaction temperature is 320-390 ℃ and the reaction pressure is 5.0-10.0MPa.
Further, the group VIB metal sulfide in the above semi-sulfided catalyst is 2.2 wt.% to 33 wt.%, preferably 10 wt.% to 20 wt.%, and the group VIII metal oxide is 0.2 wt.% to 12 wt.%, preferably 3 wt.% to 6 wt.%, based on the total weight of the catalyst.
Further, the carrier of the semi-sulfided catalyst is porous inorganic refractory oxide, more specifically, one or more selected from silica, alumina, magnesia, zirconia, titania, silica alumina, magnesia silica and magnesia alumina, and most preferably alumina. The carrier can be modified according to the need, for example, the carrier is modified by adopting B, P, F and other modifying elements, and the weight percentage of the modifying elements is 0.5-10wt% based on the weight of the modified hydrogenation catalyst carrier.
Further, the semi-sulfided catalyst is prepared by the following method:
(1) Impregnating the carrier with an impregnating solution containing a group VIB metal, drying and vulcanizing;
(2) Impregnating the product of step (1) with an impregnation solution containing a group VIII metal, followed by drying and calcination under an inert atmosphere to obtain the semi-sulfided catalyst.
Further, in the preparation method of the semi-sulfidation catalyst, the preparation method of the impregnation liquid of the group VIB metal in the step (1) is well known to those skilled in the art, for example, phosphate or ammonium salt solution is generally adopted, and the mass concentration of the impregnation liquid is 0.1g/mL to 2.0g/mL, and an equal volume impregnation mode can be adopted. The drying conditions are as follows: drying at 90-200deg.C for 3-6 hr. The vulcanization treatment is well known to those skilled in the art, and dry vulcanization or wet vulcanization is usually adopted, wherein the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12h.
Further, in the preparation method of the semi-sulfided catalyst, the preparation method of the impregnation liquid of the VIII family metal in the step (2) is well known to the person skilled in the art, for example, nitrate, acetate, sulfate solution and the like are generally adopted, the mass concentration of the impregnation liquid is 0.1 g/mL-1.0 g/mL, and the impregnation liquid can be impregnated in an equal volumeMode(s). The inert atmosphere is N 2 And one or more of inert gases; the drying temperature is 20-90 ℃ and the drying time is 4-16 hours; the roasting temperature is 200-500 ℃ and the roasting time is 2-5 hours.
Further, in the start-up method, after the vulcanization is completed, the circulation of the gas phase hydrogenation reaction product is stopped, and the gas-liquid separation is carried out to separate a gas phase product and a liquid phase product; the gas phase product can be recycled to the inlet of the reactor after desulfurization and denitrification to recycle hydrogen in the gas phase product, hydrogenation reaction is carried out again, and the liquid phase product is refined diesel oil.
Compared with the prior art, the invention has the following advantages:
(1) The semi-vulcanized catalyst is applied to the gas-phase hydrogenation process of diesel oil, the independent vulcanization process is not carried out, but the materials of the reaction product at the start-up stage are circulated, the hydrogen sulfide in the semi-vulcanized catalyst is utilized to carry out vulcanization treatment, the effective utilization of bad substances is realized, the condition of the vulcanization process is mild, and the reduction of the activity of the catalyst caused by overhigh local temperature in the vulcanization process is effectively restrained.
(2) The startup method does not need the switching between the vulcanization process and the hydrogenation reaction process, prevents the temperature runaway of the vulcanization process device, has relatively mild reaction of the semi-vulcanization catalyst with lower initial activity, can reduce the temperature rise of the gas phase reaction to a certain extent, and reduces the operation risk of the device.
(3) The semi-vulcanized catalyst is prepared by dipping the VIB group metal on the carrier in a stepwise dipping and vulcanizing mode of different active metals, and then dipping the VIII group metal, so that the VIII group metal is covered on the surface of the VIB group metal in a vulcanized state, the function of the VIII group metal auxiliary agent is fully exerted, the interaction condition between the VIB group metal auxiliary agent and the VIII group metal auxiliary agent is created, the generation of II type active centers is promoted, and the catalyst has higher activity after complete vulcanization in use.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Semi-sulfided catalysts were prepared in examples 1-4:
example 1
Ammonium molybdate is regulated by ammonia water until the ammonium molybdate is completely dissolved, then the alumina carrier is impregnated in an equal volume, and the alumina carrier is dried for 3 hours at 130 ℃. Then using a solution containing 1.5% H 2 S, hydrogen is vulcanized, the vulcanization temperature is 320 ℃, the vulcanization pressure is 4.6MPa, the vulcanization time is 10h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving cobalt nitrate in deionized water, at N 2 An atmosphere medium volume impregnated into the catalyst precursor, then in N 2 Drying for 4h at 90 ℃ and roasting for 3h at 320 ℃ under the atmosphere to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: 17.8% of molybdenum sulfide, 4.3% of cobalt oxide and the balance of carrier.
Example 2
Ammonium heptamolybdate was dissolved in deionized water and then isovolumetric impregnated into a phosphorus modified alumina support and dried at 150 ℃ for 2 hours. Then use a composition containing 3.0% CS 2 The aviation kerosene is vulcanized at 360 ℃, the vulcanization pressure is 5.4MPa, the vulcanization time is 13h, and then the aviation kerosene is vulcanized in N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving nickel nitrate in deionized water at N 2 An atmosphere medium volume impregnated into the catalyst precursor, then in N 2 Drying for 4h at 110 ℃ and roasting for 3h at 350 ℃ under the atmosphere to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: 18.2% of molybdenum sulfide, 4.6% of nickel oxide and the balance of carrier.
Example 3
Ammonium metatungstate is dissolved in deionized water, then is immersed in boron modified alumina carrier in an equal volume, and is dried for 3 hours at 160 ℃. Then use a composition containing 3.0% CS 2 The aviation kerosene is vulcanized, the vulcanization temperature is 350 ℃, the vulcanization pressure is 6.4MPa, the vulcanization time is 12 hours,then at N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving nickel nitrate in deionized water at N 2 An atmosphere medium volume impregnated into the catalyst precursor, then in N 2 Drying for 4h at 120 ℃ and roasting for 3h at 320 ℃ under the atmosphere to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: 19.2% of tungsten sulfide, 3.6% of nickel oxide and the balance of carrier.
Example 4
Ammonium metatungstate is dissolved in deionized water, then is immersed in boron modified alumina carrier in an equal volume, and is dried for 3 hours at 120 ℃. Then use a composition containing 3.0% CS 2 The aviation kerosene is vulcanized at 300 ℃ under 6.4MPa for 16 hours, and then is vulcanized in N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor. Dissolving cobalt nitrate in deionized water, at N 2 An atmosphere medium volume impregnated into the catalyst precursor, then in N 2 Drying for 4h at 110 ℃ and roasting for 3h at 350 ℃ under the atmosphere to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: 18.5% of tungsten sulfide, 4.2% of cobalt oxide and the balance of carrier.
Comparative example 1
Dissolving ammonium metatungstate into deionized water, immersing the solution into an alumina carrier in an equal volume, drying the solution for 3 hours at 120 ℃, and roasting the solution for 3 hours at 360 ℃ to obtain a catalyst precursor. Cobalt nitrate is dissolved in deionized water, is immersed in a catalyst precursor in an equal volume, is dried for 4 hours at 120 ℃ and is roasted for 4 hours at 330 ℃ to obtain the catalyst CS-1.
The catalyst CS-1 comprises the following components in percentage by weight: 18.5% of tungsten oxide, 4.2% of cobalt oxide and the balance of carrier.
Comparative example 2
Dissolving phosphomolybdic acid and nickel nitrate into deionized water, immersing the solution into an alumina carrier in an equal volume, drying the solution for 3 hours at 150 ℃, and roasting the solution for 3 hours at 360 ℃ to obtain the catalyst CS-2.
The catalyst CS-2 comprises the following components in percentage by weight: 17.8% of molybdenum oxide, 4.6% of nickel oxide and the balance of carrier.
Example 5
The catalysts prepared in the above examples and comparative examples were subjected to a gas phase hydrogenation reaction:
the adopted evaluation raw oil is mixed diesel oil provided by a petroleum refinery, the sulfur content of the raw oil is 13000-14000 mug/g, and the nitrogen content is 300-600 mug/g.
The catalysts C-1 to C-4 and comparative examples CS-1 to CS-2 were evaluated for the performance of hydrodesulfurization and denitrification reactions, respectively, using a 200mL fixed bed vapor phase hydrogenation apparatus.
Reaction conditions of the catalyst: the mixed diesel oil is used at the airspeed of 1.5h -1 The reaction temperature is 350 ℃, the hydrogen-oil volume ratio is 500:1, the catalyst is presulfided under the operation pressure of 7.0MPa, the reaction product is recycled to the inlet of the reactor, and the catalyst is further sulfided by utilizing hydrogen sulfide generated in the reactant until the sulfur content in the liquid-phase product is less than 10 mug/g, the nitrogen content is less than 2.0 mug/g, and the sulfiding is completed. Then stopping the circulation of the gas phase hydrogenation reaction product, and performing gas-liquid separation on the gas phase hydrogenation reaction product to separate a gas phase product and a liquid phase product; the gas phase product is recycled to the inlet of the reactor after desulfurization and denitrification to recycle hydrogen in the gas phase product, hydrogenation reaction is carried out again, and the liquid phase product is refined diesel oil. Each index of refined diesel oil was measured, and desulfurization rate and single removal rate were calculated, and the results are shown in Table 1.
Table 1.
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Claims (9)

1. A diesel oil hydroprocessing method using a semi-sulfided catalyst, comprising the following: mixing and heating a diesel raw material and hydrogen, introducing the mixture into a hydrogenation reactor for gas-phase hydrogenation reaction, filling a semi-vulcanization catalyst in the hydrogenation reactor, circulating a gas-phase hydrogenation reaction product to an inlet of the hydrogenation reactor, vulcanizing the semi-vulcanization catalyst by utilizing hydrogen sulfide in the product until vulcanization is completed, and stopping circulating the gas-phase hydrogenation reaction product;
the reaction conditions in the hydrogenation reactor at the start-up stage are as follows: the reaction temperature is 320-390 ℃ and the reaction pressure is 5.0-10.0Mpa;
the semi-sulfidation catalyst comprises a carrier and a hydrogenation active component, wherein the hydrogenation active component is a VIB group metal sulfide and a VIII group metal oxide; based on the total weight of the catalyst, the weight of the VIB group metal sulfide is 2.2-33 wt% and the weight of the VIII group metal oxide is 0.2-12 wt%;
the semi-sulfided catalyst is prepared by the following method:
(1) Impregnating the carrier with an impregnating solution containing a group VIB metal, drying and vulcanizing;
(2) Impregnating the product of step (1) with an impregnation solution containing a group VIII metal, followed by drying and calcination under an inert atmosphere to obtain the semi-sulfided catalyst.
2. The diesel hydroprocessing method according to claim 1, characterized in that the group VIB metal is Mo and/or W and the group VIII metal is Co and/or Ni.
3. The diesel hydro-start-up method of claim 1, wherein the feedstock diesel is one or more of straight run diesel, coker diesel, and catalytic diesel.
4. The diesel hydroprocessing method according to claim 1, wherein the sulfidation is completed under conditions that the sulfur content in the liquid phase product is less than 10ppm and the nitrogen content is less than 2.0ppm.
5. The method for starting up diesel oil according to claim 1, wherein the semi-sulfided catalyst comprises 10wt% to 20wt% of group VIB metal sulfide and 3wt% to 6wt% of group VIII metal oxide based on the total weight of the catalyst.
6. The diesel hydroprocessing method according to claim 1, wherein the support of the semi-sulfided catalyst is selected from one or more of silica, alumina, magnesia, zirconia, titania, silica alumina, magnesia silica and magnesia alumina.
7. The diesel oil hydrogenation start-up method according to claim 1, wherein the impregnating solution of the VIB group metal in the step (1) is a phosphate or ammonium salt solution, and the mass concentration of the impregnating solution is 0.1 g/mL-2.0 g/mL.
8. The method for starting up the diesel oil hydrogenation process according to claim 1, wherein the impregnating solution of the VIII family metal in the step (2) is nitrate, acetate or sulfate solution, and the mass concentration of the impregnating solution is 0.1 g/mL-1.0 g/mL.
9. The method for starting up the diesel hydrogenation process according to claim 1, wherein after the completion of the vulcanization, the circulation of the gaseous hydrogenation reaction product is stopped, and the gaseous and liquid separation is performed to separate the gaseous product and the liquid product; the gas phase product is recycled to the inlet of the reactor after desulfurization and denitrification to recycle hydrogen in the gas phase product, hydrogenation reaction is carried out again, and the liquid phase product is refined diesel oil.
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CN103059968A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Vulcanization startup method of hydrocracking device
CN104593050A (en) * 2013-11-03 2015-05-06 中国石油化工股份有限公司 Operating method for vulcanized hydrogenation catalyst
CN104593051A (en) * 2013-11-03 2015-05-06 中国石油化工股份有限公司 startup method of sulfuration type hydrogenation catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102041043A (en) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 Method for processing vulcanized hydrogenation catalyst
CN103059968A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Vulcanization startup method of hydrocracking device
CN104593050A (en) * 2013-11-03 2015-05-06 中国石油化工股份有限公司 Operating method for vulcanized hydrogenation catalyst
CN104593051A (en) * 2013-11-03 2015-05-06 中国石油化工股份有限公司 startup method of sulfuration type hydrogenation catalyst

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