CN107999092B - Vulcanization type hydrogenation catalyst, preparation method thereof and gasoline hydrodesulfurization method - Google Patents

Vulcanization type hydrogenation catalyst, preparation method thereof and gasoline hydrodesulfurization method Download PDF

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CN107999092B
CN107999092B CN201610930809.3A CN201610930809A CN107999092B CN 107999092 B CN107999092 B CN 107999092B CN 201610930809 A CN201610930809 A CN 201610930809A CN 107999092 B CN107999092 B CN 107999092B
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metal component
active metal
precursor
hydrogenation catalyst
active
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CN107999092A (en
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刘锋
褚阳
李明丰
李会峰
习远兵
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

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

Abstract

The invention relates to the field of hydrorefining and discloses a vulcanized hydrogenation catalyst, a preparation method thereof and a gasoline hydrodesulfurization method, wherein in the vulcanized hydrogenation catalyst, the atomic ratio of an active metal component A to the sum of the active metal component A and the active metal component B is more than 0.3, the content of a II-type active phase A-B-S is more than 55%, and the preparation method comprises the following steps: the mol ratio of the precursor of the active metal component A to the precursor of the active metal component B is 0.6-2.3: 1, the precursor of the active metal component B is ammonium thiosulfate. The sulfuration type hydrogenation catalyst provided by the invention is applied to the gasoline hydrodesulfurization process, and the mercaptan can be effectively removed under the condition of low octane number loss even under the condition of low reaction temperature and reaction pressure.

Description

Vulcanization type hydrogenation catalyst, preparation method thereof and gasoline hydrodesulfurization method
Technical Field
The invention relates to the field of hydrofining, in particular to a preparation method of a hydrogen sulfide hydrogenation catalyst, a sulfide hydrogenation catalyst prepared by the method and a gasoline hydrodesulfurization method.
Background
At present, air pollution causes more and more serious environmental problems, and tail gas emitted by automobile engines becomes a main source of urban air pollution. SO is generated after sulfur in gasoline is combustedxThe method has the advantages that serious pollution is caused to air, strict limitation is provided for the sulfur content in gasoline in all countries of the world, the step of limitation on the sulfur content in gasoline in China is gradually accelerated, the clean gasoline standard similar to the European III emission standard is implemented at the end of 2009, and similar standards are implemented in 2014 nationwideSimilar to the clean gasoline standard of the Euro IV emission standard, the clean gasoline emission standard similar to the Euro V emission standard is implemented nationwide in 2017, and the sulfur content in the gasoline is required to be not higher than 10 mug/g. Under the background, researchers develop clean gasoline production technologies to meet market demands.
In China, the proportion of the catalytic cracking gasoline in a gasoline pool is relatively high, and the sulfur content of the catalytic cracking gasoline is high, so that the removal of sulfur in the catalytic cracking gasoline is the most urgent problem. The most difficult sulfur in the catalytically cracked gasoline is thiophene sulfide, and the sulfur can be removed by improving the hydrogenation reaction conditions in the prior art, but the catalytically cracked gasoline contains a large amount of olefins which are high-octane components in the gasoline, and the severe hydrogenation reaction conditions easily cause olefin saturation and octane number loss, so that the olefin saturation is reduced to the maximum extent while the sulfide in the catalytically cracked gasoline is removed.
Researchers found that in the process of producing clean gasoline with sulfur content less than 10 mug/g, the remaining sulfides which are not completely removed are mainly thiol compounds, the thiol compounds are generated by addition reaction of hydrogen sulfide generated after thiophene hydrodesulfurization and olefins in gasoline, the reaction is a reversible reaction which is difficult to remove due to thermodynamic equilibrium, and if a conventional hydrodesulfurization catalyst is used to remove thiols, very harsh reaction conditions are required, which inevitably causes a great loss of octane number.
US6231754B1 discloses a process for mercaptan removal from naphtha by mercaptan decomposition with a partially deactivated catalyst (2-40% active as fresh catalyst) at high reaction temperature, which can exert the catalyst activity at high reaction temperature (305 ℃ and 455 ℃) without olefin hydrogenation saturation and has better selectivity for mercaptan removal. The disclosed method has the disadvantages of high reaction temperature, high investment and energy consumption of the device.
US6387249B1 discloses a process for removing mercaptans from naphtha by decomposing mercaptans from naphtha using a CoMo catalyst under conditions of high reaction temperature and low reaction pressure, the high reaction temperature being thermodynamically favorable for removal of mercaptans and suppression of the regeneration reaction of mercaptans, and the low reaction pressure being favorable for suppression of the regeneration reaction of mercaptans. The disclosed method has the disadvantages of high reaction temperature, high investment and energy consumption of the device.
CN101376822A discloses a gasoline sweetening catalyst, which comprises the following components in percentage by weight: 20-50 wt% of copper oxide and 50-80 wt% of zinc oxide, wherein the weight ratio of copper oxide to zinc oxide is 2:1-1:4, and the BET specific surface area is 30-60m2Per g, pore volume of 0.1-025cm3(ii)/g, the average pore diameter is 10-25 nm. The mercaptan can be removed by adopting the catalyst on the basis of small octane number loss.
Although the prior method improves the mercaptan removal activity and selectivity of the hydrogenation catalyst to a certain extent, the improvement degree is limited, and the reaction conditions are harsh. Therefore, there is a need to develop a hydrogenation catalyst with higher mercaptan removal activity and better selectivity under mild reaction conditions.
Disclosure of Invention
Aiming at the defects of low mercaptan removal activity, poor selectivity and harsh reaction conditions of the hydrogenation catalyst in the prior art, the invention provides a novel vulcanization type hydrogenation catalyst, a preparation method thereof and a gasoline hydrodesulfurization method. The catalyst provided by the invention can effectively remove mercaptan in gasoline under mild reaction conditions and low octane number loss conditions.
The invention provides a vulcanization type hydrogenation catalyst, which comprises a carrier, and an active metal component A and an active metal component B which are loaded on the carrier, wherein the active metal component A is selected from at least one of VIII group metal elements, the active metal component B is selected from at least one of VIB group metal elements, the active metal component A and the active metal component B exist in a sulfide form, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B in the catalyst measured by an X-ray fluorescence spectrum is more than 0.3, and the content of II active phases A-B-S in the catalyst measured by an X-ray electron energy spectrum is more than 55%, wherein the content of the II active phases A-B-S refers to the content of the active metal component A existing in the form of the II active phases A-B-S and the active metal component B measured by the X-ray electron energy spectrum Ratio of the total amount of the metal component A.
The invention provides a preparation method of a vulcanized hydrogenation catalyst, which comprises the following steps:
(1) dipping the carrier by a solution containing a precursor of an active metal component A and a precursor of an active metal component B, wherein the active metal component A is selected from VIII group metal elements, and the active metal component B is selected from VIB group metal elements;
(2) vulcanizing the solid material obtained after impregnation in the step (1);
wherein, the mol ratio of the precursor of the active metal component A to the precursor of the active metal component B is 0.6-2.3: 1;
the precursor of the active metal component B is ammonium thiosulfate.
The invention also provides a vulcanized hydrogenation catalyst prepared by the preparation method.
The invention also provides a gasoline hydrodesulfurization method, which comprises the following steps: the gasoline fraction is contacted with a catalyst for reaction, and the catalyst is the sulfuration type hydrogenation catalyst provided by the invention.
The inventor of the invention discovers through research that when the atomic ratio of the VIII group metal element to the sum of the VIII group metal element and the VIB group metal element in the catalyst is more than 0.3 and the content of the II-type active phase formed by the VIII group metal and the VIB group metal and sulfur is more than 55%, the catalyst has higher activity and selectivity for removing mercaptan under mild conditions. That is, when the atomic ratio of Co (Ni)/[ Co (Ni) + Mo (W) ] is 0.3 or more and the content of the II-type active phase Co (Ni) -Mo (W) -S is 55% or more, the catalyst has excellent performance. The reason for this is that the co (ni) -mo (w) -S active phase is an active center with the highest mercaptan removal/formation selectivity in the catalyst, and when the number of atoms of co (ni)/[ co (ni) + mo (w) is relatively high, it is more favorable to exert the promoter effect of co (ni) atoms, and when the number of atoms of molybdenum and/or tungsten in the catalyst is constant, the higher the atomic ratio of co (ni)/[ co (ni) + mo (w)) in the catalyst is, and the higher the measured co (ni) — mo (w) -S active phase ratio is, the higher the ratio of the type ii active phase co ni) — mo (w) -S in the catalyst is in the active phases, the higher the mercaptan removal/formation selectivity of the catalyst is. The high content of the II-type active phase Co (Ni) -Mo (W) -S indicates that Co (Ni) atoms occupy specific positions in a sulfide structure of Mo (W) to form the II-type active phase Co (Ni) -Mo (W) -S, and the II-type active phase Co (Ni) -Mo (W) -S has more excellent activity and selectivity in the mercaptan removal process. In addition, the inventor of the present invention found in the research process that when an ammonium thiosulfate salt is used as a precursor of a group VIB metal, the addition of a specific active metal component a and an active metal component B is beneficial to increasing the atomic ratio of a group VIII metal element to a group VIII metal element and a group VIB metal element and the content of a class ii active phase, and this may be because when the ammonium thiosulfate salt is used as a precursor of a group VIB metal, the promoter effect of the group VIII metal is more beneficial to be exerted, so that the group VIII metal is more easily inserted into the side of a group VIB metal sulfide crystal to generate more co (ni) -mo (w) -S active centers, while other general group VIB metal salts cannot accept insertion of promoters in the case of higher atomic ratio of co (ni)/co (ni) + mo (w), so that a high Co (Ni) -Mo (W) -S active phase ratio cannot be obtained. Specifically, the ammonium thiosulfate firstly forms molybdenum and/or tungsten intermediate sulfides on the surface of the carrier, and during the vulcanization process, the molybdenum and/or tungsten intermediate sulfides are easier to be vulcanized, so that the molybdenum and/or tungsten is vulcanized before the cobalt and/or nickel, when the molybdenum and/or tungsten is vulcanized to a certain degree, the cobalt and/or nickel also start to be vulcanized, and the cobalt and/or tungsten are subjected to synergistic action to form a Co (Ni) -Mo (W) -S active phase more easily, so that the utilization rate of active metals is improved, and the performance of the catalyst is effectively improved.
The sulfuration type hydrogenation catalyst provided by the invention is applied to the gasoline hydrodesulfurization process, and the mercaptan can be effectively removed under the condition of low octane number loss even under the condition of low reaction temperature and reaction pressure.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a sulfide type hydrogenation catalyst, which comprises a carrier, and an active metal component A and an active metal component B which are loaded on the carrier, wherein the active metal component A is selected from at least one of VIII group metal elements, the active metal component B is selected from at least one of VIB group metal elements, and the active metal component A and the active metal component B exist in a sulfide form, wherein in the catalyst, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B is more than 0.3, which is measured by an X-ray fluorescence spectrum, and in the catalyst, the content of II active phases A-B-S is more than 55%, which is measured by an X-ray electron spectrum, wherein the content of the II active phases A-B-S refers to the amount of the active metal component A existing in the form of the II active phases A-B-S and the content of the active metal component B in the form of the II active phases A-B-S, which is measured by the X-ray electron spectrum Ratio of the total amount of the active metal component A.
In the present invention, preferably, the active metal component a is a cobalt and/or nickel element, and the active metal component B is a molybdenum and/or tungsten element, and in order to further improve the activity and selectivity of the catalyst for removing mercaptans, it is further preferable that the active metal component a is a cobalt element, and the active metal component B is a molybdenum element.
The carrier is not particularly limited in the present invention, and may be any of various carriers commonly used in the art, and may be commercially available or may be prepared by any method known in the art, and in order to further improve the activity and selectivity of the hydrogenation catalyst for removing mercaptans, it is preferable that the carrier is a heat-resistant inorganic oxide.
Preferably, the heat-resistant inorganic oxide is selected from one or more of alumina, silica, titania, magnesia, silica-alumina, silica-magnesia, alumina-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia, most preferably alumina.
In the context of the present invention, the active phase class II A-B-S is the active center of the hydrogenation catalyst, the concept being proposed by Haldor Topsoe in 1984. In the hydrogenated catalyst after being vulcanized, VIII group metal elements exist in different forms, for example, Co is taken as an example, in the vulcanized CoMo catalyst, Co is respectively Co2+Co-Mo-S and Co9S8The Co existing in different forms corresponds to peaks at different positions in the XPS spectrogram, and the Co is calculated by unfolding the peaks2+Co-Mo-S and Co9S8Corresponding peak area by Co-Mo-S corresponding peak area/(Co)2+Corresponding peak area + Co-Mo-S corresponding peak area + Co9S8Corresponding peak area) x 100%, the content of the II-type active phase Co-Mo-S is calculated, and the method is also suitable for NiW catalysts. The specific calculation method can be found in Qielimei article (X-ray photoelectron spectroscopy is used to study the chemical state of active elements in hydrodesulfurization catalyst [ J]And petroleum science and newspaper: petroleum processing, 2011, 27 (4): 638-642).
In the present invention, X-ray photoelectron spectroscopy (XPS) was carried out on an ESCA Lab 250 type X-ray photoelectron spectrometer (VG, UK) without specific description, and was obtained under the conditions that the radiation source was Al K.alpha., the resolution was 0.5eV, and the internal standard was the binding energy of C1s contaminated with carbon (Eb 285.0 eV).
In the present invention, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B is given by the result of X-ray fluorescence spectrum analysis.
In the present invention, X-ray fluorescence spectroscopy (XRF) analysis was carried out using a ZSX-100e type X-ray fluorescence spectrometer using an Rh target at a current of 50mA and a voltage of 50kV, unless otherwise specified.
According to a preferred embodiment of the present invention, the atomic ratio of the active metal component a to the sum of the active metal component a and the active metal component B is 0.3 to 0.7, more preferably 0.4 to 0.7, most preferably 0.4 to 0.6; the content of the active phase A-B-S of group II is 55 to 95%, more preferably 60 to 90%, most preferably 70 to 80%. The mercaptan removal activity and selectivity of the catalyst can be further improved by adopting the preferred embodiment.
The atom ratio of the active metal component A to the active metal component A and the active metal component B in the gasoline sweetening catalyst disclosed by the prior art is less than 0.3, and the content of the II active phase A-B-S is below 50 percent and mostly between 40 and 50 percent.
According to the sulfided hydrogenation catalyst provided by the invention, the content of the carrier is preferably 70-97 wt%, and more preferably 79-93 wt% based on the total amount of the catalyst; the content of the active metal component A is 1 to 10% by weight, more preferably 1 to 6% by weight, and the content of the active metal component B is 2 to 20% by weight, more preferably 6 to 15% by weight, in terms of oxide.
The invention also provides a preparation method of the vulcanized hydrogenation catalyst, which comprises the following steps:
(1) dipping the carrier by a solution containing a precursor of an active metal component A and a precursor of an active metal component B, wherein the active metal component A is selected from VIII group metal elements, and the active metal component B is selected from VIB group metal elements;
(2) vulcanizing the solid material obtained after impregnation in the step (1);
wherein, the mol ratio of the precursor of the active metal component A to the precursor of the active metal component B is 0.6-2.3: 1;
the precursor of the active metal component B is ammonium thiosulfate.
The selection of the active metal component A, the active metal component B and the carrier in the invention is as described above, and the details are not repeated here.
In the present invention, preferably, when the active metal component B is molybdenum element, the precursor of the active metal component B is ammonium thiomolybdate; when the active metal component B is tungsten element, the precursor of the active metal component B is ammonium thiotungstate.
According to the method provided by the invention, preferably, the active metal component B is molybdenum element, and the precursor of the active metal component B is ammonium thiomolybdate.
According to the method provided by the invention, the impregnation method in the step (1) is not particularly limited, and a co-impregnation method or a step-by-step impregnation method can be adopted, namely, the precursor of the active metal component A and the precursor of the active metal component B are prepared into a solution to impregnate the carrier together, or the solution containing the precursor of the active metal component A is impregnated into the carrier firstly, then dried and then impregnated by the precursor solution containing the active metal component B, and similarly, the active metal component B can be impregnated firstly and then impregnated. The invention preferably prepares a precursor solution containing an active metal component B to impregnate the carrier, dries the carrier, and then adopts the precursor solution containing the active metal component A to impregnate the carrier.
The impregnation conditions in the step (1) are not particularly limited in the present invention, and may be, for example, 4 to 8 hours at room temperature.
In order to further improve the mercaptan removal activity and selectivity of the catalyst, the concentration of the precursor of the active metal component B in the solution in the step (1) is preferably 0.05-1.5mol/L, more preferably 0.12-1.12mol/L, and still more preferably 0.45-1.12 mol/L.
According to the invention, the molar ratio of the precursor of the active metal component a to the precursor of the active metal component B is preferably 0.6 to 1: 1, more preferably 0.6 to 0.8: 1. with this preferred embodiment, it is more beneficial to increase the atomic ratio of the active metal component a to the active metal component a and the active metal component B of the catalyst produced.
In order to further improve the mercaptan removal activity and selectivity of the catalyst, the solution in the step (1) preferably further contains an organic complexing agent. The presence of the organic complexing agent can control the size of the metal active phase to a certain extent, and in the subsequent vulcanization process, the active metal component A is promoted to be vulcanized after the active metal component B, so that the active metal component A can more easily exert the auxiliary effect.
In the present invention, it is preferable that the molar ratio of the organic complexing agent to the precursor of the active metal component B in terms of the metal element is 0.5 to 1.5: 1, more preferably 0.6 to 1.2: 1.
the organic complexing agent can be prepared into a solution impregnation carrier together with a precursor of the active metal component A and a precursor of the active metal component B, can also be prepared into a solution impregnation carrier together with the precursor of the active metal component A or the precursor of the active metal component B, and can also be independently prepared into a solution impregnation carrier. The organic complexing agent is preferably introduced by formulating it into a solution with the precursor of the active metal component a.
The type of the organic complexing agent is not particularly limited in the present invention, and may be various organic complexing agents used in the preparation process of the hydrogenation catalyst, and for example, the organic complexing agent may be at least one selected from the group consisting of citric acid, ethylenediaminetetraacetic acid (EDTA), ethylene glycol, glycerol, and nitrilotriacetic acid.
In the present invention, the solid material in the step (2) can be obtained by drying the mixed material obtained by the impregnation in the step (1), the drying conditions are not particularly limited, and the drying can be performed in a conventional manner in the art, and the drying is preferably vacuum drying. For example, the temperature of the vacuum drying may be 60 to 150 ℃ and the time may be 2 to 10 hours.
In the present invention, the vulcanization mode in the step (2) is not particularly limited, and may be dry (gas phase) vulcanization or wet (liquid phase) vulcanization.
If dry vulcanization is adopted, the dry vulcanization can be specifically as follows: and (2) carrying out contact reaction on a sulfur-containing medium and the solid material obtained in the step (1).
According to a preferred embodiment of the present invention, the sulfur-containing medium is a mixed gas containing hydrogen and hydrogen sulfide, preferably, the mixed gas has a hydrogen sulfide content of 0.1 to 10 vol%, a hydrogen content of 90 to 99.9 vol%, further preferably, a hydrogen sulfide content of 1 to 5 vol%, a hydrogen content of 95 to 99 vol%, more preferably, a hydrogen sulfide content of 1 to 3 vol%, and a hydrogen content of 97 to 99 vol%.
In the present invention, the mixed gas may further contain an inert gas, and preferably, the mixed gas contains 0.1 to 10 vol% of hydrogen sulfide, 10 to 30 vol% of hydrogen, and 60 to 89.9 vol% of an inert gas, and further preferably, contains 1 to 3 vol% of hydrogen sulfide, 20 to 30 vol% of hydrogen, and 67 to 79 vol% of an inert gas.
In the present invention, the inert gas may be one or more selected from nitrogen, argon, helium, carbon dioxide and water vapor, preferably one or more selected from nitrogen, argon and helium, and more preferably nitrogen.
In the present invention, the conditions of the contact reaction in the dry vulcanization are not particularly limited, and preferably the conditions of the contact reaction include: the temperature is 20-400 ℃, the pressure is 0.1-20MPa, the time is 1-48h, and the volume ratio of the gas agent is 10-1000; further preferably, the temperature is 100-400 ℃, the pressure is 0.1-10MPa, the time is 5-24h, and the volume ratio of the gas agent is 20-500; more preferably, the temperature is 300-350 ℃, the pressure is 0.1-3.2MPa, the time is 5-10h, and the volume ratio of the gas agent is 50-400.
If wet vulcanization is employed, the wet vulcanization may specifically be: and (2) carrying out contact reaction on vulcanized oil containing a vulcanizing agent and the solid material obtained in the step (1) in the presence of hydrogen.
In the present invention, the vulcanizing agent is selected from a wide range, and may be, for example, at least one of elemental sulfur, inorganic sulfur compounds, mercaptans, sulfides, disulfides and polysulfides, which are generally used in the art.
In the present invention, the content of the vulcanizing agent is not particularly limited as long as sufficient vulcanization of the catalyst is satisfied, and the content of the vulcanizing agent is preferably 2 to 10 parts by weight, and more preferably 2 to 5 parts by weight, relative to 100 parts by weight of the vulcanizing oil containing the vulcanizing agent.
In the present invention, the selection range of the vulcanized oil is wide, and for example, the vulcanized oil can be selected from at least one of gasoline distillate, aviation kerosene distillate and diesel oil distillate, preferably selected from at least one of straight-run gasoline distillate, straight-run aviation kerosene distillate and straight-run diesel oil distillate, and more preferably selected from straight-run gasoline distillate; the vulcanized oil can also be selected from at least one of organic hydrocarbon substances with carbon number of 5-18, preferably from at least one of organic hydrocarbon substances with carbon number of 6-12, and more preferably cyclohexane and/or n-heptane.
In the present invention, the conditions of the contact reaction in the wet vulcanization are not particularly limited, and preferably the conditions of the contact reaction include: the temperature is 20-400 ℃, the pressure is 0.1-20MPa, the time is 1-48h, and the space velocity of hydrogen volume is 5-10000h-1The volume ratio of hydrogen to oil is 10-1000; further preferably, the temperature is 100--1The volume ratio of hydrogen to oil is 20-500; more preferably, the temperature is 300-350 ℃, the pressure is 1.6-3.2MPa, the time is 5-10h, and the hydrogen volume space velocity is 300-1600h-1The volume ratio of hydrogen to oil is 50-400.
In the present invention, wet vulcanization is preferably employed. The preferred embodiment can effectively control the size of the metal active phase, thereby further improving the activity and selectivity of the catalyst.
The hydrogenation catalyst prepared by the preparation method has excellent activity and selectivity for removing mercaptan, so the invention also provides a vulcanization type hydrogenation catalyst prepared by the preparation method.
The invention also provides a gasoline hydrodesulfurization method, which comprises the following steps: the gasoline fraction is contacted with a catalyst for reaction, and the catalyst is the sulfuration type hydrogenation catalyst provided by the invention.
The method provided by the invention is used for hydrodesulfurization of various gasoline fractions, and preferably the gasoline fractions are catalytic cracking gasoline.
In the present invention, it is preferred that the gasoline fraction has an olefin content of 10 to 60% by weight and a mercaptan content of 0.0006 to 0.015% by weight.
In the present invention, the conditions of the contact reaction are not particularly limited, and from the viewpoint of reaction energy consumption and device protection, the conditions of the contact reaction preferably include: the reaction temperature is 120-300 ℃, the reaction pressure is 0.1-2MPa, the volume ratio of hydrogen to oil is 10-400, and the volume space velocity of gasoline fraction is 1-10h-1Further preferably, the conditions of the contact reaction include: the reaction temperature is 150 ℃ and 260 ℃, the reaction pressure is 0.3-0.8MPa, the volume ratio of hydrogen to oil is 50-400, and the volume space velocity of gasoline fraction is 2-8h-1。
The catalyst provided by the invention can effectively remove mercaptan in gasoline under mild conditions, and the catalyst provided by the prior art has high reaction temperature of over 330 ℃ and harsh reaction conditions in the mercaptan removal process, so that the process application is not facilitated.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples, the metal content of the catalyst, the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B, were measured by X-ray fluorescence spectroscopy (XRF) using a ZSX-100e type X-ray fluorescence spectrometer using an Rh target at a current of 50mA and a voltage of 50 kV.
The content of the II active phase A-B-S in the catalyst is obtained by XPS data processing, and the specific processing method can be seen in literature X-ray photoelectron spectroscopy to research the chemical state [ J ] of active elements in the hydrodesulfurization catalyst, and the Petroleum science reports: petroleum processing, 2011, 27 (4): 638-642. Among them, X-ray photoelectron spectroscopy (XPS) was performed on an ESCA Lab 250 type X-ray photoelectron spectrometer (VG, england) obtained under the conditions of Al K α as a radiation source, 0.5eV as a resolution, and 285.0eV as a binding energy of C1s contaminated with carbon as an internal standard.
In the following examples, the support was a clover type alumina strip support having a circumscribed circle diameter of 1.4 mm, available from Changling catalyst division.
Example 1
(1) Weighing 25.4g of ammonium thiomolybdate, adding deionized water to prepare 110mL of aqueous solution, soaking 100g of carrier by using the aqueous solution for 6h, and then drying at 120 ℃ for 4h in vacuum to obtain Mo/Al2O3；
(2) 22.1g of cobalt nitrate and 21.55g of EDTA are weighed, deionized water is added to prepare 80mL of solution, and Mo/Al is impregnated2O36h, then dried in vacuum at 120 ℃ for 4h to obtain the oxidation state CoMo/Al2O3；
(3) Para oxidation state CoMo/Al2O3Carrying out wet vulcanization, wherein the specific conditions comprise: in the presence of hydrogen, the oxidation state CoMo/Al2O3Reacting with cyclohexane containing 5 weight percent of carbon disulfide for 6 hours at 300 ℃ and 2.4MPa, wherein the volume space velocity of hydrogen is 1600 hours-1And when the volume ratio of hydrogen to oil is 400, cooling the reaction temperature to room temperature to obtain the vulcanized hydrogenation catalyst S-1.
The contents of the components of the S-1 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 2
(1) Weighing 31.8g of ammonium thiomolybdate, adding deionized water to prepare 110mL of aqueous solution, soaking 100g of carrier by using the aqueous solution for 6h, and then drying at 120 ℃ for 4h in vacuum to obtain Mo/Al2O3；
(2) 22.1g of cobalt nitrate and 14.2g of citric acid are weighed, deionized water is added to prepare 80mL of solution, and Mo/Al is impregnated2O36h, then dried in vacuum at 120 ℃ for 4h to obtain the oxidation state CoMo/Al2O3；
(3) Para oxidation state CoMo/Al2O3Carrying out wet vulcanization, wherein the specific conditions comprise: in the presence of hydrogen, the oxidation state CoMo/Al2O3The catalyst is contacted with straight-run gasoline distillate containing 3 weight percent of carbon disulfide for reaction for 10 hours at 320 ℃ and 3.2MPa, and the volume space velocity of hydrogen is 600 hours-1Hydrogen to oil volume ratio of 300And when the reaction temperature is reduced to room temperature, obtaining the vulcanization type hydrogenation catalyst S-2.
The contents of the components of the S-2 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 3
(1) Weighing 12.69g of ammonium thiomolybdate, adding deionized water to prepare 110mL of aqueous solution, soaking 100g of carrier by using the aqueous solution for 6h, and then drying at 120 ℃ for 4h in vacuum to obtain Mo/Al2O3；
(2) Weighing 15.8g of cobalt nitrate and 6.9g of nitrilotriacetic acid, adding deionized water to prepare 80mL of solution, and soaking Mo/Al2O36h, then dried in vacuum at 120 ℃ for 4h to obtain the oxidation state CoMo/Al2O3；
(3) Para oxidation state CoMo/Al2O3Carrying out wet vulcanization, wherein the specific conditions comprise: in the presence of hydrogen, the oxidation state CoMo/Al2O3The catalyst is contacted with straight-run gasoline distillate containing 2 weight percent of dimethyl disulfide (DMDS) for reaction for 5 hours at the temperature of 350 ℃ and the pressure of 1.6MPa, and the volume space velocity of hydrogen is 300 hours-1And when the volume ratio of hydrogen to oil is 200, cooling the reaction temperature to room temperature to obtain the vulcanized hydrogenation catalyst S-3.
The contents of the components of the S-3 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 4
The process described in example 1 was followed except that ammonium thiomolybdate, cobalt nitrate and EDTA were co-formulated as a solution to impregnate the support, specifically:
(1) weighing 25.4g of ammonium thiomolybdate, 22.1g of cobalt nitrate and 21.55g of EDTA21, adding deionized water to prepare 110mL of aqueous solution, soaking 100g of carrier in the aqueous solution for 6 hours, and then drying the carrier in vacuum at 120 ℃ for 4 hours to obtain oxidation state CoMo/Al2O3；
(2) Para oxidation state CoMo/Al2O3Carrying out wet vulcanization, wherein the specific conditions comprise: in the presence of hydrogen, the oxidation state CoMo/Al2O3Reacting with cyclohexane containing 5 weight percent of carbon disulfide for 6 hours at 300 ℃ and 2.4MPa, wherein the volume space velocity of hydrogen is 1600 hours-1Hydrogen to oil volume ratio of 400, to be reactedAnd cooling to room temperature to obtain the sulfide hydrogenation catalyst S-4.
The contents of the components of the S-4 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 5
The process as in example 1 except that the vacuum drying in step (1) and step (2) was replaced by drying in air at the same temperature for a certain time so that Mo/Al was dried2O3And CoMo/Al2O3Respectively dried in vacuum with the Mo/Al in the example 12O3And CoMo/Al2O3The masses are equal.
The sulfuration type hydrogenation catalyst S-5 is obtained by the method.
The contents of the components of the S-5 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 6
The process according to example 1 is followed, except that the vulcanization is carried out by dry vulcanization, in particular:
(1) weighing 25.4g of ammonium thiomolybdate, adding deionized water to prepare 110mL of aqueous solution, soaking 100g of carrier by using the aqueous solution for 6h, and then drying at 120 ℃ for 4h in vacuum to obtain Mo/Al2O3；
(2) 22.1g of cobalt nitrate and 21.55g of EDTA are weighed, deionized water is added to prepare 80mL of solution, and Mo/Al is impregnated2O36h, then dried in vacuum at 120 ℃ for 4h to obtain the oxidation state CoMo/Al2O3；
(3) Para oxidation state CoMo/Al2O3Carrying out dry vulcanization, wherein the specific conditions comprise:
by H2S and H2Mixed gas (H) of (2)2S volume content of 1%) as sulfur-containing medium, and CoMo/Al in oxidation state2O3And (3) carrying out contact reaction for 6h at the temperature of 300 ℃ and the pressure of 2.4MPa, wherein the volume ratio of the gas agent is 400, and obtaining the vulcanization type hydrogenation catalyst S-6 when the reaction temperature is reduced to room temperature.
The contents of the components of the S-6 sulfided hydrogenation catalyst and the results of XPS analysis are shown in Table 1.
Example 7
According to the method of example 1, except that no organic complexing agent EDTA was added, a sulfided hydrogenation catalyst S-7 was obtained, and the contents of the components of the sulfided hydrogenation catalyst S-7 and the results of XPS analysis are shown in Table 1.
Example 8
According to the procedure of example 1, except for replacing ammonium thiomolybdate with the same mass of ammonium thiotungstate and replacing cobalt nitrate with the same mass of nickel nitrate, a sulfided hydrogenation catalyst S-8 was obtained, and the contents of the components of the sulfided hydrogenation catalyst S-8 and the results of XPS analysis are shown in Table 1.
Comparative example 1
According to the procedure of example 1, except that ammonium thiomolybdate was replaced with the same mass of ammonium heptamolybdate based on the molybdenum element, a sulfided hydrogenation catalyst D-1 was obtained, and the contents of the components of the sulfided hydrogenation catalyst D-1 and the results of XPS analysis are shown in Table 1.
Comparative example 2
According to the procedure of example 1, except that the amount of ammonium thiomolybdate added was 25.4g, the amount of cobalt nitrate added was 13.2g, and the amount of EDTA added was 12.8g, sulfided hydrogenation catalyst D-2 was obtained, and the contents of the components of sulfided hydrogenation catalyst D-2 and the results of XPS analysis are shown in Table 1.
TABLE 1 catalyst component content and XPS analysis results
Figure BDA0001137923110000161
Test examples
In this test example, the mercaptan removal activity and selectivity of the sulfided hydrogenation catalyst provided in the inventive example and the hydrogenation catalyst provided in the comparative example were evaluated in accordance with the following methods and are intended to demonstrate the beneficial effects of using the catalyst provided in the present invention for the hydrodesulfurization of gasoline.
The catalyst performance was evaluated on a small fixed bed hydrogenation reactor using 1-hexene, octane, and a 100. mu.g/g solution of 1-heptanethiol (the volume ratio of 1-hexene to octane was 20:80) as a model compound for gasoline. The reaction conditions are as follows: 1.6The hydrogen-oil volume ratio is 400 at the MPa of 260 ℃ and the volume space velocity is 8h-1. After the reaction is stable for 3h, sampling and analyzing after the reaction is carried out for 4 h. The samples were analyzed by GC-MASS and the results are shown in Table 2. Wherein, the olefin saturation rate HYD, the removal rate X of heptanethiol (for explaining the activity of mercaptan removal), the concentration Y of hexanethiol sulfur (namely, sulfur existing in the form of hexanethiol) and the hexanethiol formation factor S (for explaining the selectivity of mercaptan removal, the lower the S, the better the selectivity of mercaptan removal) of the reaction are calculated according to the following formula:
HYD ═ 100%
X ═ raw heptanethiol concentration-product heptanethiol concentration)/raw heptanethiol concentration X100%
Y-percent hexanethiol concentration in the product x 0.2712 x 10000
S＝Y/(100-HYD)
TABLE 2
Examples HYD/％ X/％ Y/(μg/g) S
Example 1 68.5 100 9.4 0.3
Example 2 72 100 10 0.36
Example 3 49.3 100 10.2 0.20
Example 4 70.5 100 12.1 0.41
Example 5 69.3 100 15.1 0.49
Example 6 70 100 13.1 0.44
Example 7 64.2 100 13.9 0.39
Example 8 60.5 100 15 0.38
Comparative example 1 66.4 99 19.1 0.57
Comparative example 2 67.5 97 21.8 0.67
The results in tables 1 and 2 show that, compared with the hydrogenation catalyst prepared by the conventional method, the sulfided hydrogenation catalyst provided by the invention can realize effective removal of mercaptan even if the sulfided hydrogenation catalyst has similar metal composition under milder reaction conditions, and has low olefin saturation rate and low mercaptan generation factor S, which indicates that the sulfided hydrogenation catalyst prepared by the method provided by the invention has high mercaptan removal activity and good selectivity, and the preparation method provided by the invention has incomparable superiority compared with the conventional impregnation method. As can be seen from a comparison of example 1 with examples 4 and 6, the performance of the hydrogenation catalyst can be further improved by employing the preferred sulfiding and impregnation method of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (15)

1. A method for preparing a sulfided hydrogenation catalyst, the method comprising:
(1) dipping the carrier by a solution containing a precursor of an active metal component A and a precursor of an active metal component B, wherein the active metal component A is selected from VIII group metal elements, and the active metal component B is selected from VIB group metal elements;
(2) vulcanizing the solid material obtained after impregnation in the step (1);
wherein, the mol ratio of the precursor of the active metal component A to the precursor of the active metal component B is 0.6-2.3: 1;
the precursor of the active metal component B is ammonium thiosulfate;
wherein, the impregnation mode is as follows: dipping the carrier by using a precursor solution containing an active metal component B, drying, and then dipping by using a precursor solution containing an active metal component A; the drying is vacuum drying;
wherein, the content of the carrier in the vulcanization type hydrogenation catalyst is 70-97 wt% based on the total amount of the catalyst; calculated by oxide, the content of the active metal component A is 1-10 wt%, and the content of the active metal component B is 2-20 wt%;
wherein, in the catalyst prepared by the preparation method: the atomic ratio of the active metal component A to the sum of the active metal component A and the active metal component B is more than 0.42 through X-ray fluorescence spectrum detection, and the content of the II type active phase A-B-S is more than 73% through X-ray electron energy spectrum detection, wherein the content of the II type active phase A-B-S refers to the ratio of the amount of the active metal component A existing in the II type active phase A-B-S form to the total amount of the active metal component A measured by X-ray electron energy spectrum.
2. The method for preparing a sulfided hydrogenation catalyst as claimed in claim 1, wherein the concentration of the precursor of the active metal component B in the solution in step (1) is 0.05-1.5 mol/L.
3. The method for preparing a sulfided hydrogenation catalyst as claimed in claim 1, wherein the precursor of the active metal component B in the solution has a concentration of 0.12-1.12mol/L in the step (1).
4. The method for preparing a sulfided hydrogenation catalyst as claimed in claim 1, wherein the molar ratio of the precursor of active metal component a to the precursor of active metal component B is 0.6-1: 1.
5. the method for preparing a sulfided hydrogenation catalyst according to claim 4, wherein the solution in step (1) further contains an organic complexing agent, and the molar ratio of the organic complexing agent to the precursor of the active metal component B calculated by the metal element is 0.5-1.5: 1.
6. the method of claim 5, wherein the organic complexing agent is at least one selected from the group consisting of citric acid, ethylenediaminetetraacetic acid, ethylene glycol, glycerol, and nitrilotriacetic acid.
7. The process for preparing a sulphided hydrogenation catalyst according to any of claims 1 to 6, wherein sulphiding the solid material in step (2) comprises: and (3) under the vulcanization condition, the solid material is contacted with a vulcanization medium for reaction.
8. The method of preparing a sulfided hydrogenation catalyst as described in claim 7, wherein the sulfiding conditions comprise: the sulfuration temperature is 20-400 ℃, the sulfuration pressure is 0.1-20MPa, the sulfuration time is 1-48h, the volume ratio of hydrogen to oil is 10-1000, and the volume space velocity of hydrogen is 5-10000h-1。
9. The method of claim 7, wherein the sulfiding media is selected from at least one of elemental sulfur, inorganic sulfur compounds, mercaptans, and thioethers.
10. The production method according to any one of claims 1 to 6, wherein the active metal component A is an element of cobalt and/or nickel, and the active metal component B is an element of molybdenum and/or tungsten.
11. The production method according to any one of claims 1 to 6, wherein the active metal component A is an element of cobalt and the active metal component B is an element of molybdenum.
12. The production method according to any one of claims 1 to 6, wherein the precursor of the active metal component B is ammonium thiomolybdate.
13. A sulfided hydrogenation catalyst prepared by the method of any one of claims 1-12.
14. A gasoline hydrodesulfurization process comprising: a gasoline fraction is contacted with a catalyst for reaction, characterized in that the hydrogenation catalyst of sulfided type as claimed in claim 13.
15. The gasoline hydrodesulfurization process of claim 14 wherein the conditions for contacting the gasoline fraction with the catalyst comprise: the reaction temperature is 120-300 ℃, the reaction pressure is 0.1-2MPa, the volume ratio of hydrogen to oil is 10-400, and the volume space velocity of gasoline fraction is 1-10h-1。
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