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CN112705225B - Oil silicon capturing agent and preparation method thereof - Google Patents

Oil silicon capturing agent and preparation method thereof Download PDF

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Publication number
CN112705225B
CN112705225B CN201911020775.4A CN201911020775A CN112705225B CN 112705225 B CN112705225 B CN 112705225B CN 201911020775 A CN201911020775 A CN 201911020775A CN 112705225 B CN112705225 B CN 112705225B
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silicon
group metal
agent
oil
capturing agent
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CN112705225A (en
Inventor
杨成敏
周勇
刘丽
段为宇
李扬
姚运海
郭蓉
孙进
郑步梅
丁莉
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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
    • B01J23/002—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
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • 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
    • B01J37/024—Multiple impregnation or coating
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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

Abstract

The invention discloses an oil silicon capturing agent and a preparation method thereof. The oil product silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide; based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.1-12.2 wt%, the VIB group metal oxide accounts for 0.5-17.2 wt%, the VIII group metal oxide accounts for 0.1-9.0 wt%, and the carrier accounts for 61.6-90.3%. The preparation method comprises the following steps: (1) Dipping the silicon catching agent carrier by using dipping solution containing VIII group metal, then drying, and vulcanizing the dried material; (2) By containing groups VIB and

Description

Oil silicon capturing agent and preparation method thereof
Technical Field
The invention relates to a silicon capturing agent for coking naphtha and a preparation method thereof.
Background
The coking naphtha hydrofining technology can remove or partially remove impurities such as silicon, olefin, sulfur, nitrogen, aromatic hydrocarbon and the like in the raw materials, and the products can be used as fuel gasoline and chemical raw materials. The implementation of the technology can convert low-value coker naphtha into high value-added products.
Coker naphtha contains a significant amount of silicon which deposits on the hydrofinishing catalyst, resulting in catalyst deactivation. In order to slow or avoid silicon poisoning deactivation of the hydrofinishing catalyst, a silicon trap is typically loaded into the inlet portion of the reactor.
At present, the development direction of the silicon capturing agent is to improve the desiliconization capability and the silicon containing capability.
CN101343565A discloses a hydrofining method of silicon-containing distillate oil. The hydrogenation catalyst with the silicon capturing function has larger pore volume and specific surface area and relatively lower metal content. CN102051202A discloses a silicon capturing agent for coking naphtha and application thereof. The silicon capturing agent takes alumina as a carrier, silicon dioxide as an auxiliary agent and W, mo and Ni as hydrogenation components. CN103920524A discloses a desiliconization agent, a preparation method and an application thereof. The desiliconization agent contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier is pseudo-boehmite and a mesoporous Y-type molecular sieve. The improvement of the silicon capturing agent of the above patent is mainly focused on the carrier, and the improvement of the active component of the catalyst is less involved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an oil silicon capturing agent and a preparation method thereof. The active components in the silicon capturing agent have higher activity and better silicon containing capacity, and are suitable for the desiliconization and silicon capturing treatment of silicon-containing oil products such as coking dry gas, coking naphtha, coking diesel oil and the like.
The oil product silicon capturing agent comprises a carrier and hydrogenation active components, wherein the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide, wherein the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni; the weight of the VIII group metal sulfide is 0.1-12.2 wt%, preferably 0.4-6.8 wt% based on the total weight of the silicon capturing agent; group VIB metal oxides from 0.5wt% to 17.2wt%, preferably from 1.6wt% to 9.3wt%; 0.1wt% to 9.0wt%, preferably 0.2wt% to 2.0wt%, calculated as group VIII metal oxide; the carrier is 61.6% -90.3%.
The silicon capturing agent is subjected to vulcanization and then is analyzed by XPS energy spectrum, wherein the molar ratio of the +4 valence VIB group metal content to the total VIB group metal content is 70-100%. Typical vulcanization process conditions are: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more 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.
The carrier is a porous inorganic refractory oxide, is selected from one or more oxides of elements in II group, III group, IV group and IVB group of the periodic table, is more preferably selected from one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide and aluminum magnesium oxide, and is further preferably aluminum oxide. The silicon capturing agent carrier can be modified according to the needs, for example, modification elements such as B, P, F and the like are adopted for modification, and the weight percentage of the modification elements is 0.5-10 wt% based on the weight of the modified hydrogenation catalyst carrier. The silicon capturing agent carrier can also partially adopt other crushed catalyst powder, such as a hydrocracking catalyst containing silicon oxide and a hydrocracking catalyst containing a molecular sieve.
The preparation method of the oil silicon capturing agent comprises the following steps:
(1) Dipping the silicon catching agent carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material;
(2) With a catalyst containing groups VIB and VIB
Figure DEST_PATH_IMAGE001
And (3) dipping the vulcanized material obtained in the step (1) in a dipping solution of the group metal, and then drying and roasting the dipped material in an inert atmosphere to obtain the oil silicon catching agent.
In the method of the present invention, the preparation method of the impregnation solution of the group VIII metal in step (1) is well known to those skilled in the art, and for example, ammonium molybdate, ammonium metatungstate solution, etc. can be used, and an equal volume impregnation or other impregnation method can be used. The first mentioned
Figure 309384DEST_PATH_IMAGE001
The group metals are preferably Ni and/or Co.
In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.
In the method of the present invention, the vulcanization treatment in step (1) is well known to those skilled in the art, and usually adopts dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide; the vulcanizing pressure is 3.2-6.4MPa, the vulcanizing temperature is 250-400 ℃, and the vulcanizing time is 4-12 hours.
In the process of the present invention, the groups VIB and VIB in step (2) are
Figure 447104DEST_PATH_IMAGE001
The impregnation solution of the group metals is well known to those skilled in the art, and for example, nitrate, acetate, sulfate solutions and the like are generally used, and the impregnation with equal volume or other impregnation method can be adopted, wherein the group VIB metal is preferably Mo and/or W, and the second group metal is preferably Mo and/or W
Figure 987938DEST_PATH_IMAGE001
The group metals are preferably Ni and/or Co.
In the method of the invention, the inert atmosphere in the step (2) is N 2 And an inert gas; 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.
The oil silicon capturing agent is applied to the processes of coking dry gas hydrogenation, coking naphtha hydrogenation, reforming prehydrogenation, coking diesel oil hydrogenation and the like.
The oil silicon capturing agent of the invention needs to be vulcanized before application, and the general vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanizing pressure is 3.2-6.4MPa, the vulcanizing temperature is 250-400 ℃, and the vulcanizing time is 4-12 hours.
The traditional catalyst exists in an oxidation state before vulcanization, the edges, corners and edges of a carrier of the traditional catalyst are fewer, the oxidation state active components on the catalyst correspondingly have fewer edges, corners and edges after being converted into a vulcanization state through the vulcanization process, and the traditional catalyst has larger active phase wafers, lower metal utilization rate and lower reaction activity. The inventor develops a new method, by the way of dipping and vulcanizing different active metals step by step, firstly dipping the VIII family metal on the carrier and vulcanizing in advance, and then dipping the VIB family and the VIB family on the sulfide
Figure 335743DEST_PATH_IMAGE001
A group metal. The stepwise impregnation enables the first
Figure 72755DEST_PATH_IMAGE001
Group metal sulfides are distributed on the surface of the alumina carrier, so that the number of edges, corners and edge positions is increased, and a smaller active phase wafer is formed in the vulcanization stage of the next-step dipped VIB group metal in the start-up process; the VIII group element in the second dipping process can disperse the VIB group element in the dipping process, so that the size of the active phase wafer is further reduced, and the activity of the silicon capturing agent is further improved. The silicon capturing agent can reduce the quantity of active components, increase the pore volume and the specific surface area of a finished catalyst product and improve the desiliconization and silicon capturing performances of the finished catalyst product due to the improvement of the performance of the active components.
Detailed Description
The method has the characteristics that the desilication and silicon capturing performance of the silicon capturing agent is enhanced by improving the utilization rate of the hydrogenation component, the hydrogenation component with lower content is used, and higher specific surface area and pore volume are reserved.
The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The catalyst composition provided by the invention is characterized by inductively coupled plasma ICP, a transmission electron microscope and XPS energy spectrum. The catalyst provided by the invention has metal vulcanization degree of Mo 4+ Or W 4+ The content represents the degree of metal sulfidation of the catalyst. Using 30mL/min of H at 320 DEG C 2 S vulcanization 2h, an XPS spectrometer represents the metal valence state of the surface of a sample, XPSPEAK version4.0 is adopted to respectively carry out fitting peak separation on Mo3d, W4f, co2p and Ni2p energy spectrums, and the metal vulcanization degree is obtained through calculation according to the peak area. Using 30mL/min of H at 320 DEG C 2 S sulfurizing for 2h, and characterizing the morphology of the active phase of the sample by a transmission electron microscope, wherein the morphology is 10000nm 2 WS in the above area 2 /MoS 2 And (5) counting the average lamellar length and the average stacking layer number.
Example 1
An alumina carrier was immersed in an aqueous cobalt nitrate solution in an equal volume so that the CoO content of the primary semifinished product was 0.3% (using the analysis after calcination at 470 ℃ as a standard), and then dried at 100 ℃ for 3 hours to obtain a primary semifinished product A1. Then sulfurizing A1 by dry sulfurization to convert the metal into Co 9 S 8 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 260 ℃ and under the pressure of 3.7MPa to obtain a semi-finished product A2. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium molybdate and cobalt nitrate to perform equal-volume impregnation on A2, so that MoO is newly added to the latter 3 5.0% (analysis after baking at 470 ℃ is taken as standard) and 0.6% (analysis after baking at 470 ℃ is taken as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, baking at 340 ℃ for 3 hours to obtain Co 9 S 8 -MoO 3 -CoO/Al 2 O 3 Catalyst A3.
Example 2
An equal volume of aqueous nickel nitrate solution was impregnated onto the alumina support to give a first-stage semi-finished product with a NiO content of 1.7% (using 470 ℃ C. As a standard for analysis after calcination), and then dried at 150 ℃ for 4 hours to give a first-stage semi-finished product B1. Then vulcanizing B1 by adopting dry vulcanizationIn which the metal is converted to Ni 2 S 3 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 300 ℃ and under the pressure of 4.1MPa to obtain a semi-finished product B2. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium molybdate and nickel nitrate to perform isovolumetric impregnation on B2, so that MoO is newly added to the latter 3 7.0% (analysis after baking at 470 ℃ is taken as a standard) and 0.3% (analysis after baking at 470 ℃ is taken as a standard), drying at 85 ℃ for 5 hours in a nitrogen atmosphere, and baking at 340 ℃ for 3 hours to obtain Ni 2 S 3 -MoO 3 -NiO/Al 2 O 3 And a catalyst B3.
Example 3
The nickel nitrate aqueous solution was immersed in an equal volume on the alumina support so that the NiO content on the primary semi-finished product was 3.1% (using 470 ℃ roasting analysis as a standard), and then dried at 190 ℃ for 3 hours to obtain a primary semi-finished product C1. Then sulfurizing C1 by dry sulfurization to convert the metal into Ni 2 S 3 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 390 ℃ and under the condition of 6.3MPa to obtain a semi-finished product C2. Under the protection of nitrogen, adopting mixed aqueous solution of ammonium molybdate and nickel acetate to perform equal-volume impregnation on C2, so that MoO is newly added in the latter 3 17.0% (using 470 ℃ roasting analysis as standard) and NiO content 1.9% (using 470 ℃ roasting analysis as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, roasting at 340 ℃ for 3 hours to obtain Ni 2 S 3 -MoO 3 -NiO/Al 2 O 3 Catalyst C3.
Example 4
In SiO 2 The siliceous alumina support with a content of 4.6% was immersed in an aqueous nickel nitrate solution in equal volume so that the NiO content on the first-stage semifinished product was 5.6% (using the analysis after calcination at 470 ℃ as a standard), and then dried at 180 ℃ for 3 hours to obtain a first-stage semifinished product D1. Then D1 is vulcanized by dry vulcanization to convert the metal into Ni 2 S 3 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 360 ℃ and under the pressure of 5.0MPa to obtain a semi-finished product D2. Under the protection of nitrogen, D2 is subjected to isovolumetric impregnation by adopting a mixed aqueous solution of ammonium molybdate and cobalt nitrate, so that MoO is newly added in the latter 3 15.0% (analysis after baking at 470 ℃ is taken as standard) and 2.5% (analysis after baking at 470 ℃ is taken as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, baking at 340 ℃ for 3 hours to obtain Ni 2 S 3 -MoO 3 -CoO/Al 2 O 3 -SiO 2 Catalyst D3.
Example 5
In SiO 2 Impregnating a siliceous alumina carrier with the content of 7.3% with nickel acetate aqueous solution in equal volume to ensure that the NiO content on the first-stage semi-finished product is 8.0% (taking analysis after roasting at 470 ℃ as a standard), and then drying at 160 ℃ for 3 hours to obtain a first-stage semi-finished product E1. Then sulfurizing E1 by dry sulfurization to convert the metal into Ni 2 S 3 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at the temperature of 350 ℃ and under the pressure of 4.9MPa to obtain a semi-finished product E2. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium metatungstate and nickel acetate to perform equal-volume impregnation on E2, so that WO is newly added to the latter 3 13.0% (taking analysis after roasting at 470 ℃ as a standard) and 4.0% of NiO (taking analysis after roasting at 470 ℃ as a standard), drying at 85 ℃ for 5 hours in a nitrogen atmosphere, and roasting at 340 ℃ for 3 hours to obtain Ni 2 S 3 -WO 3 -NiO/Al 2 O 3 -SiO 2 Catalyst E3.
Example 6
In SiO 2 The siliceous alumina carrier with the content of 3.3 percent is dipped into nickel acetate aqueous solution with equal volume, so that the NiO content on the first-stage semi-finished product is 11.0 percent (taking the analysis after being roasted at 470 ℃ as a standard), and then the first-stage semi-finished product F1 is obtained after being dried for 4 hours at 170 ℃. Then sulfurizing F1 by dry sulfurization to convert the metal into Ni 2 S 3 And vulcanizing the mixture for 5 hours by using hydrogen with the hydrogen sulfide content of 2 percent at 330 ℃ under the condition of 4.2MPa to obtain a semi-finished product F2. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium metatungstate and nickel acetate to perform equal-volume impregnation on F2, so that WO is newly added to the latter 3 10.0% (using 470 ℃ roasting analysis as standard) and NiO content 8.0% (using 470 ℃ roasting analysis as standard), then drying at 85 ℃ for 5 hours in nitrogen atmosphere, roasting at 340 ℃ for 3 hours to obtain Ni 2 S 3 -WO 3 -NiO/Al 2 O 3 -SiO 2 Catalyst F3.
Example 7
Mixing 12% of mixed hydrocracking catalyst powder into alumina powder, granulating, drying and roasting to obtain SiO 2 Content of 3.5%, WO 3 The carrier has the content of 1.6 percent and the NiO content of 0.4 percent (taking the analysis after roasting at 470 ℃ as the standard). The carrier is dipped with nickel acetate aqueous solution with equal volume, so that the NiO content is newly increased by 2.7 percent (taking the analysis after roasting at 470 ℃ as the standard), and then the carrier is dried for 3 hours at 180 ℃ to obtain a section of semi-finished product F1. And then vulcanizing the F1 by adopting a dry method to convert the metal in the F1 into a corresponding metal sulfide, and vulcanizing the F2 by using hydrogen with the hydrogen sulfide content of 2 percent for 5 hours at 330 ℃ under the condition of 4.2 MPa. Under the protection of nitrogen, adopting a mixed aqueous solution of ammonium metatungstate and nickel acetate to perform equal-volume impregnation on F2, so that the latter is added with WO 3 Content of 7.0% (using 470 ℃ analysis after firing as a standard) and NiO content of 0.9% (using 470 ℃ analysis after firing as a standard), drying at 85 ℃ for 5 hours in nitrogen atmosphere, and firing at 340 ℃ for 3 hours to obtain WS 2 -Ni 2 S 3 -WO 3 -NiO/Al 2 O 3 -SiO 2 Catalyst G3.
Comparative example 1
This comparative example is compared to example 2.
Soaking ammonium molybdate and nickel nitrate aqueous solution on an alumina carrier in equal volume to ensure that MoO is coated on a section of semi-finished product 3 The content of 7.0 percent and the NiO content of 2.0 percent (both taking analysis after roasting at 470 ℃ as a standard), then drying for 4 hours at 150 ℃, roasting for 3 hours at 340 ℃ to obtain MoO 3 -NiO/Al 2 O 3 And (4) catalyst DB.
Comparative example 2
This comparative example is compared to example 5.
In SiO 2 Soaking 7.3% silicon-containing alumina carrier with ammonium metatungstate and nickel acetate aqueous solution in equal volume to obtain a semi-finished product 3 13.0 percent of NiO content and 12.0 percent of NiO content (taking the analysis after roasting at 470 ℃ as the standard)Then dried at 160 ℃ for 3 hours and calcined at 340 ℃ for 3 hours to obtain WO 3 -NiO/Al 2 O 3 -SiO 2 Catalyst DE.
Example 8
This example illustrates the reactivity of the silicon capture agent provided by the present invention to coker naphtha. Representing the influence degree of the active components on the pore volume and the specific surface area of the silicon catching agent through the specific surface area loss rate of the silicon catching agent immediately after vulcanization; the hydrogenation performance of the active component is measured by the carbon deposition amount on the silicon capturing agent after operation; the desiliconization and silicon capturing performance of the silicon capturing agent is measured by the content of saturated silicon on the silicon capturing agent after operation.
The evaluation feedstock used was coker naphtha supplied from a petrochemical refinery.
The catalysts A3 to G3, comparative examples DB and DE were subjected to the evaluation of the reaction properties using a 200mL trickle bed hydrogenation apparatus, respectively.
Presulfurizing conditions of the catalyst: using a content of 2.1wt% of CS 2 The space velocity of the aviation kerosene is 1.0h -1 The hydrogen-oil volume ratio is 360.
The prevulcanisation process is as follows: feeding pre-vulcanized oil at 100 ℃, feeding the oil for 1h, vulcanizing at constant temperature for 2h, heating to 130 ℃ at 15 ℃/h, vulcanizing at constant temperature for 4h, heating to 240 ℃ at 6 ℃/h, vulcanizing at constant temperature for 3h, heating to 260 ℃ at 6 ℃/h, vulcanizing at constant temperature for 6h, heating to 330 ℃ at 12 ℃/h, vulcanizing at constant temperature for 16h, and naturally cooling to 110 ℃, thus finishing the pre-vulcanization.
The evaluation reaction conditions were: the operating pressure is 3.4MPa, the reaction temperature is 260 ℃, and the volume space velocity is 1.6h -1 And a hydrogen-oil volume ratio 370, and the evaluation results are shown in table 1.
TABLE 1 Properties and evaluation results of catalysts
Figure DEST_PATH_IMAGE003
The above evaluation results show that the active metal of the silicon capturing agent has higher sulfidation degree, the loss of the specific surface area of the catalyst after the completion of the sulfidation is low, the carbon deposition amount is low after the operation is finished, and the saturated silicon capacity is high.

Claims (13)

1. An oil silicon capturing agent comprises a carrier and a hydrogenation active component, and is characterized in that: the hydrogenation active components are VIII group metal sulfide, VIB group metal oxide and VIII group metal oxide, wherein the VIB group metal is Mo and/or W, and the VIII group metal is Co and/or Ni; based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.1-12.2 wt%, the VIB group metal oxide accounts for 0.5-17.2 wt%, the VIII group metal oxide accounts for 0.1-9.0 wt%, and the carrier accounts for 61.6-99.3%; the preparation method of the oil silicon capturing agent comprises the following steps: (1) Dipping the silicon catching agent carrier by using dipping solution containing VIII group metal, then drying, and vulcanizing the dried material; (2) Dipping the vulcanized material in the step (1) by using a dipping solution containing metals of a VIB group and a VIII group, and then drying and roasting in an inert atmosphere to obtain an oil silicon capturing agent; the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.
2. The oil silicon capturing agent according to claim 1, characterized in that: based on the total weight of the silicon capturing agent, the VIII group metal sulfide accounts for 0.4-6.8 wt%; 1.6-9.3 wt% of VIB group metal oxide, 0.2-2.0 wt% of VIII group metal oxide and 81.9-97.8% of carrier.
3. The oil silicon capture agent of claim 1, wherein: the carrier is porous inorganic refractory oxide, and is selected from one or more oxides of elements in the IIA group, the IIIA group, the IVA group and the IVB group in the periodic table.
4. The oil silicon capturing agent according to claim 1, characterized in that: the carrier is one or more of silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, silicon aluminum oxide, silicon magnesium oxide, aluminum magnesium oxide, a hydrocracking catalyst containing silicon oxide or a hydrocracking catalyst containing a molecular sieve.
5. A method for preparing the oil silicon catching agent according to any one of claims 1 to 4, which is characterized by comprising the following steps: (1) Dipping the silicon catching agent carrier by using dipping liquid containing VIII group metal, then drying, and vulcanizing the dried material; (2) Dipping the vulcanized material in the step (1) by using a dipping solution containing metals of a VIB group and a VIII group, and then drying and roasting in an inert atmosphere to obtain an oil silicon capturing agent; the drying conditions in the step (1) are as follows: the drying temperature is 90-200 ℃, and the drying time is 3-6 hours.
6. The method of claim 5, wherein: the VIII group metal in the step (1) is Ni and/or Co.
7. The method of claim 5, wherein: the vulcanization treatment in the step (1) adopts dry vulcanization or wet vulcanization; wherein the dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide or n-butyl sulfide.
8. The method of claim 5, wherein: the vulcanization treatment conditions in the step (1) are as follows: the vulcanizing pressure is 3.2-6.4MPa, the vulcanizing temperature is 250-400 ℃, and the vulcanizing time is 4-12 hours.
9. The method of claim 5, wherein: the VIB group metal in the step (2) is Mo and/or W; the group VIII metal is Ni and/or Co.
10. The method of claim 5, wherein: the inert atmosphere in the step (2) is N 2 And an inert gas; 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.
11. The oil silicon capturing agent as defined in any one of claims 1 to 4, which is applied to hydrogenation of coking dry gas, hydrogenation of coking naphtha, reforming prehydrogenation and hydrogenation of coking diesel oil.
12. Use according to claim 11, characterized in that: before the application of the oil silicon capturing agent, the oil silicon capturing agent needs to be subjected to vulcanization treatment, wherein the vulcanization treatment conditions are as follows: adopting dry vulcanization or wet vulcanization, wherein the dry vulcanization agent is hydrogen sulfide, and the wet vulcanization agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanizing pressure is 3.2-6.4MPa, the vulcanizing temperature is 250-400 ℃, and the vulcanizing time is 4-12 hours.
13. Use according to claim 12, characterized in that: after the oil product silicon capturing agent is vulcanized, XPS energy spectrum analysis is adopted, wherein the molar proportion of the VIB group metal content of +4 valence state in the total VIB group metal content is 70-100%.
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