CN107456975A - A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved - Google Patents
A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved Download PDFInfo
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- CN107456975A CN107456975A CN201610390805.0A CN201610390805A CN107456975A CN 107456975 A CN107456975 A CN 107456975A CN 201610390805 A CN201610390805 A CN 201610390805A CN 107456975 A CN107456975 A CN 107456975A
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- 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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The invention discloses a kind of method pre-processed to hydrogenation catalyst and the pretreated hydrogenation catalyst obtained by this method and its application, this method includes the hydrogenation catalyst is vulcanized and activated successively, the activation is including the use of the hydrogenation catalyst after the maceration extract dipping vulcanization containing organic oxygen-containing compound, then it is heat-treated, wherein, the temperature of the heat treatment is 200 450 DEG C, and the time of heat treatment is 0.5 12 hours.Method provided by the invention can effectively improve the hydrodesulfurization performance of hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst preprocess method and improve the desulphurizing activated method of hydrogenation catalyst and
The pretreated hydrogenation catalyst obtained by this method and its application in hydrodesulfurization reaction.
Background technology
The environmental problem that motor vehicle exhaust emission is brought becomes increasingly conspicuous, and countries in the world propose more to the composition of engine fuel
Carry out more severe limitation.Sulfur content is reduced, the clean fuel that production meets environmental legislation is imperative.At present, hydrodesulfurization is
Most widely used and effective desulfurization means.Industrially, the catalyst that hydrogenation process uses usually contains VI B and group VIII
Metal (such as molybdenum, tungsten, nickel, cobalt) element, carrier are aluminum oxide or silicon-containing alumina.Freshly prepared catalyst is with oxidation state shape
Formula is present, and vulcanizing treatment need to be typically carried out carrying out hydrogenation reaction procatalyst, to obtain higher active and longer use
Life-span.
Different according to vulcanization reaction place, vulcanization can be divided into device to be vulcanized outside vulcanization and device.Vulcanization is by oxygen in device
Change introducing vulcanizing agent after state catalyst loads reactor to be vulcanized.Vulcanize to shorten compared with device vulcanizing, outside device and go into operation
Cycle.Vulcanize outside device and be divided into two kinds：Ex situ presulfiding and true vulcanization.Ex situ presulfiding refers to the vulcanizing agent dipping of sulfur atom-containing
(load) causes sulfide that certain interaction occurs with metal into oxidized catalyst through Overheating Treatment, and reloading is to instead
Answer vulcanizing agent hydrogenolysis is hydrogen sulfide in device using hydrogen so as to be the catalyst for having hydrogenation activity by catalyst vulcanization.Wherein,
The purpose of heat treatment is vulcanizing agent is produced certain effect power with metal, prevents that hydrogen sulfide is concentrated during hydrogen heating hydrogenolysis vulcanizing agent
Release concentration is too high.The advantages of ex situ presulfiding is that the outer process of device is not related to the dangerous gas such as hydrogen sulfide and hydrogen, and shortcoming is
Also need to use Hydrogen activation after being loaded into reactor, while the risk that hydrogen sulfide in activation process concentrates release also be present.
True vulcanization refers to contact oxidized catalyst with vulcanizing agent and hydrogen outside reactor, and catalyst, which is directly vulcanized to be changed into, to be had
The catalyst of activity.The advantages of true vulcanization is that Hydrogen activation need not be used after being loaded into reactor, can be introduced directly into reaction
Raw material is reacted, and on-stream time is short.
CN1107707C discloses a kind of vulcanization side using the component of olefin-containing, elementary sulfur and agent mixture as vulcanizing agent
Method.The mixture is heated at 100-220 DEG C more than 0.5 hour, the molal quantity of elementary sulfur is no less than the molal quantity of olefinic double bonds,
Auxiliary dosage is the 10-80wt% of elementary sulfur dosage, and the auxiliary agent is selected from the organic additive that the vulcanization of rubber is commonly used；The production that will be obtained
Thing dipping introduces the catalyst of elementary sulfur, and under an inert atmosphere in 100-300 DEG C of heatable catalyst more than 1 hour；Wherein, institute
The volumetric usage for stating product is at least the 60% of catalyst pore volume.The dosage of auxiliary agent is the method reduce, but process is complicated, bag
Drying, dipping and the vulcanization of catalyst are included, therefore processing time is grown.
CN101665745B relate to a kind of ex-situ presulfiding method of hyrorefining catalysts, and this method is to add vegetable oil
Powdery sulphur is slowly added to by a certain percentage after heat to certain temperature, generates red black sulfurized oil, then by a certain percentage to red black
Hydrobon catalyst is added in color sulfurized oil, is fitted into after well mixed in reactor, heats and lives with a temperature of in certain pressure
Change, be cooled to room temperature, that is, complete Hydrobon catalyst ex situ presulfiding.The catalyst vulcanized using this method can be in air
In be stabilized, be readily transported and store.
CN102284299B provides a kind of hydrogenation catalyst in hydrogenation reaction ex situ presulfiding-work in hydrogenation reactor
The method of change, using lower boiling vulcanizing agent and hydrogen or with the gaseous mixture of hydrogen and inert gas as vulcanizing agent, by oxidation state plus
Hydrogen catalyst is added to progress gas-phase presulfiding reaction in vulcanization reaction device, then introduces oxygen-containing passivating gas passivation sulphided state catalysis
Agent.Catalyst after passivation pack sealing, after transport storage, is reloaded into hydrogenation reactor, drawn by being drawn off in vulcanization reaction device
Enter the gaseous mixture of hydrogen sulfide and hydrogen, make the reactivation of catalyst after vulcanization passivation.
US6417134 relate to vulcanize new method (true vulcanization) outside a kind of device, first use liquid hydrocarbon oxide impregnation at room temperature
State catalyst, it is liquid filled 10-100% pore volumes, then in 200-500 DEG C and H2And H2S gaseous mixtures fully contact.Leaching
Liquid hydrocarbon used in stain can be oxygenatedchemicals, such as alcohol, acid, ketone, ester or vegetable oil, nitrogen-containing compound, sulfur-bearing
Compound, organic polysulfide, lube base oil, diesel oil and white oil etc..Substantial amounts of heat, liquid hydrocarbon are released in sulfidation
Play a part of carrier regenerator, prevent beds temperature runaway.
, can be to sulphur before sulfidation terminates back end hydrogenation desulphurization reaction in order to improve the catalytic performance of hydrogenation catalyst
Change state catalyst pre-process in device.US6120679 discloses a kind of method of catalytic gasoline hydrogenation desulfurization, by alkalescence
Nitrogen-containing organic compound and In-situ sulphiding CoMo/Al2O3Or NiMo/Al2O3Catalyst contacts in 200 DEG C or lower temperature,
Then heat to 250 DEG C or higher of temperature and carry out hydrodesulfurization reaction.The preprocess method can improve hydrodesulfurization selection
Property, but obvious effect is had no to desulphurizing activated raising.There is document report CoMo/Al2O3Catalyst through vulcanize and aging after,
350 DEG C, carry out carbon deposit pretreatment using 1- methyl naphthalenes, cyclohexene and ar mixture under the conditions of 0.5MPa after；With fresh catalyst
Agent is compared, and the hydrogenation of olefins activity in catalytic gasoline hydrogenation desulphurization reaction is remarkably decreased, but hydrodesulfurization activity is also bright
It is aobvious to have dropped (Industrial＆Engineering Chemistry Research, 1998,37 (5)：1748-1754.).
The content of the invention
The defects of it is an object of the invention to overcome prior art hydrodesulfurization activity relatively low, there is provided a kind of new hydrogenation is urged
The agent preprocess method method desulphurizing activated with hydrogenation catalyst is improved, urged using the pretreated hydrogenation of the method for the present invention
Agent has considerably higher hydrodesulfurization activity.
The present inventor is on the basis of lot of experiments it was unexpectedly observed that being lived after hydrogenation catalyst is vulcanized
Change, the hydrodesulfurization activity of catalyst can be significantly improved.The activation includes dipping and the heat treatment carried out successively, wherein using
Contain organic oxygen-containing compound in the maceration extract of the dipping, the temperature of the heat treatment is 200-450 DEG C, the time of heat treatment
For 0.5-12 hours, based on this, the present invention is formed.
According to the first aspect of the invention, the present invention provides a kind of method for improving hydrogenation catalyst desulfurization performance, the party
Method includes the hydrogenation catalyst is vulcanized and activated successively, and the activation is including the use of containing organic oxygen-containing compound
Hydrogenation catalyst after maceration extract dipping vulcanization, is then heat-treated, wherein, the temperature of the heat treatment is 200-450 DEG C,
The time of heat treatment is 0.5-12 hours.
According to the second aspect of the invention, should the invention provides a kind of method pre-processed to hydrogenation catalyst
Method includes the hydrogenation catalyst is vulcanized and activated successively, and the activation is including the use of containing organic oxygen-containing compound
Maceration extract dipping vulcanization after hydrogenation catalyst, be then heat-treated, wherein, the temperature of the heat treatment is 200-450
DEG C, the time of heat treatment is 0.5-12 hours.
According to the third aspect of the invention we, the invention provides the pretreated hydrogenation catalyst obtained by the above method
Agent.
According to the fourth aspect of the invention, after the pretreatment obtained the invention provides the above method and by the above method
Application of the hydrogenation catalyst in hydrodesulfurization reaction especially gasoline fraction oil hydrodesulfurization reaction.
The preprocess method of hydrogenation catalyst provided by the invention, by impregnating particular types after vulcanizing to hydrogenation catalyst
Compound and be heat-treated in specified conditions so that the desulphurizing activated of pretreated hydrogenation catalyst significantly improves.
It is hydrogenated with using the pretreated hydrogenation catalyst that method provided by the invention obtains especially suitable for gasoline fraction oil.For example,
It is can be seen that according to the result of hereinafter table 1 in the case of other conditions identical, the method using the present invention is pretreated
The hydrodesulfurization activity (HDS) of hydrogenation catalyst is 97.5% (embodiment 3), and the hydrodesulfurization activity (HDS) of comparative example 1 is
78.1%, the hydrodesulfurization activity (HDS) of comparative example 2 is only 74.2%, and the hydrodesulfurization activity (HDS) of comparative example 3 is
80.3%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Carried out according to the method provided by the invention that can improve hydrogenation catalyst desulfurization performance and to hydrogenation catalyst pre-
The method of processing, this method include the hydrogenation catalyst is vulcanized and activated successively, it is described activation including the use of containing
Hydrogenation catalyst after the maceration extract dipping vulcanization of organic oxygen-containing compound, is then heat-treated, wherein, the heat treatment
Temperature is 200-450 DEG C, and the time of heat treatment is 0.5-12 hours.
As long as although containing the i.e. achievable purpose of the present invention of organic oxygen-containing compound in maceration extract, under preferable case,
The content of organic oxygen-containing compound is 0.01-15wt% in the maceration extract.Organic oxygen-containing in the further preferred maceration extract
The content of compound is 0.1-4wt%.
The organic oxygen-containing compound can be the various organic matters containing oxygen element, preferably organic oxygen-containing compound be alcohol,
At least one of ether, phenol, acid and ester.The organic oxygen-containing compound is the monohydric alcohol and/or binary that carbon number is 2-10
Alcohol, the monohydric phenol and/or dihydric phenol and their monoether and/or bis ether that carbon number is 2-10.The alcohol for example can be
In ethanol, propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propane diols, butanediol, glycerine, pentaerythrite
It is one or more.The ether can be the one or more in dimethyl ether, ethyl methyl ether, diethyl ether, methyl phenyl ethers anisole, 1,2-dimethoxy benzene.
The phenol can be the one or more in phenol, o-cresol, xylenols, pholorol.The acid for example can be first
One or more in acid, acetic acid, propionic acid, citric acid, oxalic acid, gallic acid.The ester for example can be ethyl acetate, acetic acid
One or more in methyl esters, sec-Butyl Acetate.
Preferably, the organic oxygen-containing compound is the monohydric alcohol and/or dihydric alcohol, monohydric phenol that carbon number is 2-10
And/or dihydric phenol and their monoether and/or bis ether；It is further preferred that the organic oxygen-containing compound is ethanol, second two
One or more in alcohol, isopropanol, propane diols, glycerine, butanol, butanediol, phenol, o-cresol.
The solvent for forming the maceration extract can be the various organic and/or nothings that can dissolve above-mentioned organic oxygen-containing compound
Solvent, instantiation include but is not limited to water or petroleum ether, normal heptane, n-decane, toluene, dimethylbenzene, boiling range 40-
One or more in 360 DEG C of distillate, further preferred boiling point are 70-200 DEG C of organic solvent, the particularly preferably positive last of the ten Heavenly stems
Alkane.
The dipping is preferably incipient impregnation (i.e. hole saturation impregnates).The temperature of dipping can be selected in relative broad range
Select, such as can be carried out at 10-350 DEG C.From energy consumption and the angle of process time is saved, the temperature of dipping can be upper
The operation temperature of one step, curing temperature or passivation temperature as will be described.The time of dipping is preferably 10 minutes-
48 hours, more preferably -24 hours 30 minutes.
According to method provided by the invention, the temperature of the heat treatment is preferably 220-410 DEG C, more preferably 250-
350℃。
The time of heat treatment is preferably 1-10 hours, more preferably 2-6 hours.
The heat treatment is preferably carried out under inert gas shielding atmosphere.
In the present invention, the inert gas can in nitrogen and the periodic table of elements the 0th race's elemental gas, preferably nitrogen
One or more in gas, argon gas and helium, more preferably nitrogen.
In the present invention, by impregnating specific organic matter on hydrogenation catalyst after curing and carrying out under given conditions
Heat treatment, the hydrodesulfurization activity of catalyst can be significantly improved.Trace it to its cause is probably because vulcanizing the activity of rear catalyst
Site has been formed, so as to compared with the loading process of the organic complexing agent before vulcanization or further heat treatment process, vulcanize
The activation process specific aim carried out again afterwards is stronger, and activation degree is controllable, so as to the structural modification of active phase controllably in institute
Need position to carry out, thus reach the purpose for promoting hydrodesulfurization reaction to carry out.By on hydrogenation catalyst before and after test processes
Carbon content is understood, is added using carbon content on the hydrogenation catalyst after the method processing of the present invention.
According to method provided by the invention, the mode of the vulcanization is gas-phase presulfiding mode, specifically, the side of the vulcanization
Formula is hydrogen and the mixed gas of hydrogen sulfide is contacted with the hydrogenation catalyst.Wherein, the hydrogen and vulcanization
In the mixed gas of hydrogen, hydrogen sulfide content is preferred 0.1-25 volumes %, more preferably 0.5-8 volumes %, more preferably 1-8
Volume %.The content of hydrogen is preferably 75-99.9 volume %, preferably 92-99.5 volumes %, more preferably 92-99 volumes %.
Inert gas can also be contained in the mixed gas, one or more of the inert gas in nitrogen, argon gas and helium are excellent
Elect nitrogen as；The content of inert gas is to less than or equal to 80 volume %, preferably 1-30 volumes % more than 0.When the mixing
When containing inert gas in gas, the content of hydrogen sulfide is preferably greater than 2 volume % and is less than 8 volume %.
The temperature of the vulcanization can be 260-400 DEG C, and when the time can be 1-48, pressure can be 0.1-10MPa, mix
The volume space velocity for closing gas can be 50-2000 hours-1.Preferably, the condition of the vulcanization reaction includes：Temperature is 260-
380 DEG C, pressure 0.1-5MPa, the time is 1-24 hours, the volume space velocity 100-1000 hours of mixed gas-1。
In the present invention, the pressure refers both to gauge pressure.
In the present invention, the volume space velocity of the mixed gas of vulcanization and passivation step represents the stream of mixed gas under standard state
Measure (unit mL/h) and the ratio of the volume (unit mL) of catalyst.
A preferred embodiment of the invention, elevated the temperature by way of temperature programming to reaction needed for
Temperature, it is possible thereby to avoid occurring temperature runaway phenomenon in sulfidation.The mode of described program heating for example can be to use 0.5-
1.5h such as 1h by temperature of reactor from room temperature rise to 200-300 DEG C such as 230 DEG C after constant temperature 1-3h such as 2h, then with 1-3h examples
As temperature of reactor is risen to 320-400 DEG C such as 360 DEG C by 2h, constant temperature vulcanization is then carried out.
According to method provided by the invention, under preferable case, this method is additionally included in before activation or will be after vulcanization after activation
Hydrogenation catalyst be passivated, the catalyst after passivation has higher stability, thus allow for transport and device outside grasp
Make.In the present invention, passivation can be carried out before activation, can also after activation be carried out, be specifically dependent upon and be actually needed.For example,
If activation needs to carry out in the reactor different from vulcanization reaction device, transfer, it is necessary to carry out blunt after curing for convenience
Change, then take out, activation act is carried out outside vulcanization reaction device；If need (to be different from activation in other reactors after activation
Reactor) in carry out hydrodesulfurization reaction, then be passivated after activation.If vulcanization, activation and hydrodesulfurization reaction are same
Carried out in one reactor, catalyst need not be exposed in external environment, then without passivating process.
The mode of the passivation is to contact the hydrogenation catalyst after vulcanization with the mixed gas containing inert gas and oxygen.
Consider from passivation effect and hydrodesulfurization effect, oxygen contains in the preferably described mixed gas containing inert gas and oxygen
Measure as 0.05-10 volume %, preferably 0.1-5 volumes %.Inert gas content is 90-99.95 volume %, preferably 95-
99.9 volume %.By being passivated in the presence of appropriate oxygen, can prevent from sending out when the catalyst and air contact after vulcanization
Raw vigorous oxidation reaction, releases substantial amounts of heat and causes sintering of catalyst.
The condition bag that hydrogenation catalyst after vulcanization is contacted with the mixed gas containing inert gas and oxygen and (is passivated)
It is room temperature to 100 DEG C to include temperature, and the time be 1-48 hours, and pressure is 0.1-10 MPas, the volume space velocity 50-2000 of mixed gas
Hour-1；It is preferred that the temperature being passivated is 30-70 DEG C, pressure is 0.1-5 MPas, and the time is 1-12 hours, and the volume of mixed gas is empty
Fast 100-1000 hours-1。
Method provided by the invention is applied to various hydrogenation catalysts, it is preferable that the hydrogenation catalyst is selected from hydrogenation essence
One kind in catalyst processed, hydrotreating catalyst and hydrocracking catalyst, preferably Hydrobon catalyst.
It is further preferred that the hydrogenation catalyst, which contains carrier, organic complexing agent and at least one, is selected from VIII
Race and at least one metal component selected from vib.On the basis of the total amount of hydrogenation catalyst, the organic complexing agent contains
Amount is preferably 5-30wt%.
The carrier can be the porous heat-resistant inorganic oxide for being commonly used for catalyst carrier, preferably aluminum oxide.
The organic complexing agent is selected from any organic complexing agent beneficial to improving catalyst performance, such as organic network
Mixture can be selected from organic carboxyl acid and its ammonium salt, and the carbon number of the organic carboxyl acid is preferably C1-C10, specifically, described have
Machine carboxylic acid preferably be selected from trans 1,2- 1,2-diaminocyclohexane tetraacetic acids, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid,
One or more in formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid.
Selected from group VIII and the metal component selected from vib it is conventional selection in the catalyst, for example, described the
Group VIII metal component is selected from cobalt and/or nickel, and vib metals component is selected from molybdenum and/or tungsten, the metal of preferably described VIII
For Co, the metal of vib is Mo.
The group VIII metal component can be selected from the one or more in the soluble compound of these metals, example
Such as, it can be in these metals nitrate, acetate, carbonate, chloride, soluble complexes one or more.Institute
Stating vib metals compound can be selected from the one or more in the soluble compound of these metals, for example, it may be molybdenum
One or more in hydrochlorate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
Hydrogenation catalyst of the present invention is prepared using conventional method, including uses method customary in the art to the carrier
It is middle introducing at least one group VIII and at least one vib metals component and including or include introduce organic complex
Agent, for example, it may be at least one group VIII will be contained, at least one is selected from vib metals compound and organic network
The method that mixture is configured to impregnate after mixed solution the carrier；Can also be by containing at least one group VIII, at least one
The method that kind individually prepares impregnated carrier after solution selected from vib metals compound and organic complexing agent.Wherein, by right
The regulation and control of the concentration of the solution of metallic components, dosage or carrier dosage, can prepare the described of specified content plus
Hydrogen catalyst.
According to the present invention, after completing the step of above-mentioned impregnating metal compound and/or organic complexing agent, optionally may be used
The step such as to be dried, be calcined or not be calcined.The condition of the drying and roasting is conventional, for example, drying temperature can
Think 100-300 DEG C, preferably 100-200 DEG C, drying time can be 1-12 hours, preferably 2-8 hours；Sintering temperature can
Think 350-550 DEG C, preferably 400-500 DEG C, roasting time can be 1-10 hours, preferably 2-8 hours.
According to a kind of embodiment, method provided by the invention comprises the steps of：(1) using hydrogen and hydrogen sulfide
Mixed gas vulcanizes to the hydrogenation catalyst；(2) by step (1) obtained by sulphided state cooling catalyst, then introduce
Mixed gas containing inert gas and oxygen contacts with the sulphided state catalyst, is passivated；(3) will be urged obtained by step (2)
Agent draws off vulcanization reaction device, then solution of the incipient impregnation containing organic oxygen-containing compound；(4) in inert gas atmosphere,
Catalyst obtained by step (3) is heat-treated under higher temperature.
Present invention also offers the pretreated hydrogenation catalyst obtained by the above method.Use side provided by the invention
Method can significantly improve the desulphurizing activated of hydrogenation catalyst.
It is true sulphurized catalyst according to the catalyst after the method processing of the present invention, the catalyst warp of gained after transpassivation
Pack sealing, after transport storage, hydrogenation reactor is reloaded into, without adding the liquid or gas cure of peculiar smell and toxic
Agent is re-activated, and avoids live pollution, and shorten on-stream time.
Method provided by the invention and catalyst obtained by this method are particularly suitable for applying in hydrogenation reaction, especially
It is using hydrodesulfurization reaction as the application in main purpose hydrofining reaction.Therefore, present invention also offers the above method
With the application of the hydrogenation catalyst that is obtained by the above method in hydrodesulfurization reaction.Can be obvious using method provided by the invention
Improve the desulphurizing activated of hydrogenation catalyst.
Method provided by the invention is suitable for oil, coal liquefaction fraction oil (for example, gasoline, boat coal, diesel oil etc.) hydrogenation
Catalyst in course of reaction, the catalyst being particularly suitable for use in gasoline fraction oil hydrogenation process.The hydrogenation reaction can
To be enough to make the feedstock oil under hydrogenation conditions with carrying out in the catalytic reaction unit of the catalyst any,
For example, the reaction can be carried out in fixed bed reactors, moving-burden bed reactor or fluidized bed reactor.The present invention is to described
There is no particular limitation for the condition of hydrogenation reaction, and preferable reaction condition includes：200-420 DEG C of reaction temperature, pressure 1-15 million
Pa, liquid hourly space velocity (LHSV) 0.3-15 hours-1, hydrogen to oil volume ratio 30-5000；Reaction condition is more preferably：Reaction temperature 200-350
DEG C, 1-10 MPas of pressure, liquid hourly space velocity (LHSV) 0.3-10 hours-1, hydrogen to oil volume ratio 100-2000.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.With
In lower embodiment and comparative example, catalyst 1 used and catalyst 2 are the CoMo/Al of the citric acid containing complexing agent2O3Catalyst,
Catalyst 3 is the CoMo/Al without complexing agent2O3Catalyst, carrier are commercial alumina (Chang Ling catalyst plant).Catalyst
Preparation process is specially：Using incipient impregnation method supported active metals component, maceration extract be containing cobalt nitrate, ammonium heptamolybdate and
The ammonia spirit (ammonia concn 18wt%) of the citric acid selectively contained, impregnate after 120 DEG C of dry 3h.Catalyst 1 and 3
Content of metal be：2.8wt%CoO and 8.2wt%MoO3, the content of metal of catalyst 2 is：1.5wt%CoO and
8.2wt%MoO3；In catalyst 1 and 2, the content of citric acid is respectively 6wt% and 12wt%.
Embodiment 1
The particle 20mL of catalyst 1 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 1 in advance
Reason：
(1) 2 volume %H are used2S+98 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas volume
Air speed is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor liter
To 320 DEG C, then vulcanize 12 hours in 320 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 600h-1, 6h is purged, is passivated.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 1.2wt% at room temperature
The n-decane solution of glycerine, dip time 24h.
(4) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 6h in atmosphere.Pretreated catalyst is designated as N-1.
Embodiment 2
The particle 20mL of catalyst 1 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 1 in advance
Reason：
(1) 8 volume %H are used2S+92 volumes %H2Gaseous mixture device is raised to operating pressure 0.6MPa, gas volume
Air speed is 1000h-1, then with 1.5h by temperature of reactor from room temperature rise to 250 DEG C after constant temperature 1.5h, then with 2.5h by reactor
Temperature rises to 380 DEG C, then vulcanizes 4 hours in 380 DEG C of constant temperature.
(2) after question response device temperature is down to 30 DEG C, vulcanization autogenous cutting is changed to 5 volume %O2+ 95 volume %N2, pressure is
0.6MPa, gas volume air speed are 900h-1, 3h is purged, is passivated.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 0.2wt% at room temperature
The n-decane solution of ethylene glycol, dip time 12h.
(4) and then by gained catalyst it is placed in N2350 DEG C of heat treatment 2h in atmosphere.Pretreated catalyst is designated as N-2.
Embodiment 3
The catalyst granules 2 of 20mL diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate catalyst granules 2 in advance
Reason：
(1) 5 volume %H are used2S+95 volumes %H2Gaseous mixture device is raised to operating pressure 3MPa, gas volume is empty
Speed is 100h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h temperature of reactor is risen to
360 DEG C, then vulcanize 6 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 70 DEG C, vulcanization autogenous cutting is changed to 2.5 volume %O2+ 97.5 volume %N2, pressure
For 1MPa, gas volume air speed is 150h-1, purge 10h and be passivated.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, at room temperature incipient impregnation benzene containing 4wt%
Distillate (boiling range is 80-180 DEG C) solution of phenol, dip time 24h.
(4) and then by gained catalyst it is placed in N2300 DEG C of heat treatment 4h in atmosphere.Pretreated catalyst is designated as N-3.
Embodiment 4
Method according to embodiment 3 pre-processes to catalyst, unlike, phenol by identical weight methyl phenyl ethers anisole generation
Replace, pretreated catalyst is designated as N-4.
Embodiment 5
Method according to embodiment 3 pre-processes to catalyst, unlike, the concentration of hydrogen sulfide is in step (1)
10 volume %, pretreated catalyst are designated as N-5.
Embodiment 6
Method according to embodiment 3 pre-processes to catalyst, unlike, the concentration of hydrogen sulfide is 1 in step (1)
Volume %, pretreated catalyst are designated as N-6.
Embodiment 7
Method according to embodiment 6 pre-processes to catalyst, unlike, in step (2) atmosphere of passivation be containing
The volume %N of 10 volume % oxygen+902Atmosphere, pretreated catalyst are designated as N-7.
Embodiment 8
Method according to embodiment 6 pre-processes to catalyst, unlike, the temperature of passivation is 100 in step (2)
DEG C, pretreated catalyst is designated as N-8.
Embodiment 9
Method according to embodiment 6 pre-processes to catalyst, unlike, the concentration of phenol is 6wt%, pretreatment
Catalyst afterwards is designated as N-9.
Embodiment 10
Method according to embodiment 6 pre-processes to catalyst, unlike, the concentration of phenol is 1wt%, pretreatment
Catalyst afterwards is designated as N-10.
Embodiment 11
Method according to embodiment 6 pre-processes to catalyst, unlike, the temperature of heat treatment is in step (4)
450 DEG C, pretreated catalyst is designated as N-11.
Comparative example 1
The particle of catalyst 2 is pre-processed according to the method for embodiment 6, unlike, not including step (3) and (4),
After the passivation of step (2) terminates, gained catalyst is drawn off into vulcanization reaction device, preserved in aluminium foil valve bag.After Passivation Treatment
Catalyst be designated as CN-1.
Comparative example 2
The particle of catalyst 2 is pre-processed according to the method for embodiment 6, unlike, the temperature of step (4) heat treatment
For 500 DEG C.Pretreated catalyst is designated as CN-2.
Comparative example 3
The particle of catalyst 2 is pre-processed according to the method for embodiment 6, unlike, step (3) and (4) are in step
(1) carry out, i.e., the particle of catalyst 2 is pre-processed using following step before：
(1) by the distillate (boiling range be 80-180 DEG C) of the particle of catalyst 2 incipient impregnation phenol containing 4wt% at room temperature
Solution, dip time 24h.
(2) and then by gained catalyst it is placed in N2300 DEG C of heat treatment 4h in atmosphere.
(3) 1 volume %H is used2S+99 volumes %H2Gaseous mixture device is raised to operating pressure 3MPa, gas volume is empty
Speed is 100h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h temperature of reactor is risen to
360 DEG C, then vulcanize 6 hours in 360 DEG C of constant temperature.
(4) after question response device temperature is down to 70 DEG C, vulcanization autogenous cutting is changed to 2.5 volume %O2+ 97.5 volume %N2, pressure
For 1MPa, gas volume air speed is 150h-1, purge 10h and be passivated.Pretreated catalyst is designated as CN-3.
Embodiment 12
The particle 20mL of catalyst 1 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 1 in advance
Reason：
(1) 1.5 volume %H are used2S+98.5 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas
Volume space velocity is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by reactor temperature
Degree rises to 360 DEG C, then vulcanizes 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 1000h-1, purge 6h.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 3wt% third at room temperature
The n-decane solution of glycol, dip time 24h.
(4) and then by gained catalyst it is placed in N2300 DEG C of heat treatment 4h in atmosphere.Pretreated catalyst is designated as N-
12。
Embodiment 13
The particle 20mL of catalyst 3 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 3 in advance
Reason：
(1) 6 volume %H are used2S+94 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas volume
Air speed is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor liter
To 360 DEG C, then vulcanize 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, containing needed for incipient impregnation is passed through into vulcanization reaction device
The n-decane solution of 0.15wt% ethanol, dip time 8h.
(3) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 6h in atmosphere.
(4) after heat treatment terminates, 0.5 volume %O is passed through into reactor2+ 99.5 volume %N2Mixed gas, pressure
For 3.6MPa, gas volume air speed is 800h-1, purge 6 hours, be passivated.Pretreated catalyst is designated as N-13.
Comparative example 4
The particle of catalyst 3 is pre-processed according to the method for embodiment 13, unlike, step (3) and (4) are in step
(1) carry out, i.e., the particle of catalyst 3 is pre-processed using following step before：
(1) by the n-decane solution of the particle of catalyst 3 incipient impregnation ethanol containing 0.15wt% at room temperature, dip time
For 8h.
(2) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 6h in atmosphere.
(3) 6 volume %H are used2S+94 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas volume
Air speed is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor liter
To 360 DEG C, then vulcanize 4 hours in 360 DEG C of constant temperature.
(4) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 3.6MPa, gas volume air speed is 800h-1, 6h is purged, is passivated.After passivation terminates, gained catalyst is drawn off into vulcanization
Reactor.Pretreated catalyst is designated as CN-4.
Embodiment 14
The catalyst granules 1 of 20mL diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 1 in advance
Reason：
(1) 2 volume %H are used2S+98 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas volume
Air speed is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor liter
To 360 DEG C, then vulcanize 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 700h-1, purge 6h.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 0.15wt% at room temperature
The n-decane solution of ethanol, dip time 24h.
(4) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 2h in atmosphere.Pretreated catalyst is designated as N-
14。
Embodiment 15
The particle 20mL of catalyst 2 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 2 in advance
Reason：
(1) 2 volume %H are used2S+98 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas volume
Air speed is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor liter
To 360 DEG C, then vulcanize 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 600h-1, purge 6h.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 0.4wt% at room temperature
The n-decane solution of ethylene glycol, dip time 12h.
(4) and then by gained catalyst it is placed in N2300 DEG C of heat treatment 2h in atmosphere.Pretreated catalyst is designated as N-
15。
Embodiment 16
The particle 20mL of catalyst 1 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 1 in advance
Reason：
(1) 1.5 volume %H are used2S+98.5 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas
Volume space velocity is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by reactor temperature
Degree rises to 360 DEG C, then vulcanizes 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 600h-1, purge 6h.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 1.4wt% at room temperature
The n-decane solution of isopropanol, dip time 5h.
(4) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 6h in atmosphere.Pretreated catalyst is designated as N-
16。
Embodiment 17
The particle 20mL of catalyst 2 of diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate the particle of catalyst 2 in advance
Reason：
(1) 1.5 volume %H are used2S+98.5 volumes %H2Gaseous mixture device is raised to operating pressure 1.6MPa, gas
Volume space velocity is 500h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by reactor temperature
Degree rises to 360 DEG C, then vulcanizes 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 50 DEG C, vulcanization autogenous cutting is changed to 0.5 volume %O2+ 99.5 volume %N2, pressure
For 1.6MPa, gas volume air speed is 600h-1, purge 6h.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 0.9wt% at room temperature
The n-decane solution of isobutanol, dip time 12h.
(4) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 2h in atmosphere.Pretreated catalyst is designated as N-
17。
Embodiment 18
The catalyst granules 2 of 20mL diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate catalyst granules 2 in advance
Reason：
(1) 0.5 volume %H is used2S+99.5 volumes %H2Gaseous mixture device is raised to operating pressure 3MPa, gas body
Product air speed is 100h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then with 2h by temperature of reactor
360 DEG C are risen to, is then vulcanized 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 70 DEG C, vulcanization autogenous cutting is changed to 2.5 volume %O2+ 97.5 volume %N2, pressure
For 1MPa, gas volume air speed is 100h-1, 10h is purged, is passivated.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 2wt% bis- at room temperature
The toluene solution of methyl ether, dip time 24h.
(4) and then by gained catalyst it is placed in N2280 DEG C of heat treatment 4h in atmosphere.Pretreated catalyst is designated as N-
18。
Embodiment 19
The catalyst granules 1 of 20mL diameter 1-3 millimeters is loaded into small-sized hydrogenation test apparatus reactor flat-temperature zone, and utilized
Two parts above and below circular porcelain ball filling reactor.Then operations described below step is carried out successively to locate catalyst granules 3 in advance
Reason：
(1) 3 volume %H are used2S+90 volumes %H2+ 7 volume %N2Gaseous mixture device is raised to operating pressure 5MPa,
Gas volume air speed is 800h-1, then with 1h by temperature of reactor from room temperature rise to 230 DEG C after constant temperature 2h, then will be reacted with 2h
Device temperature rises to 360 DEG C, then vulcanizes 4 hours in 360 DEG C of constant temperature.
(2) after question response device temperature is down to 30 DEG C, vulcanization autogenous cutting is changed to 5 volume %O2+ 95 volume %N2, pressure is
5MPa, gas volume air speed are 100h-1, purge 2h and be passivated.
(3) after passivation terminates, gained catalyst is drawn off into vulcanization reaction device, incipient impregnation contains 0.7wt% at room temperature
The n-decane solution of butanediol, dip time 8h.
(4) and then by gained catalyst it is placed in N2250 DEG C of heat treatment 6h in atmosphere.Pretreated catalyst is designated as N-
19。
Embodiment 20
Method according to embodiment 19 pre-processes to catalyst, unlike, butanediol by identical weight formic acid
Instead of pretreated catalyst is designated as N-20.
Performance test example
The catalyst n -1 that above-described embodiment 1-20 and comparative example 1-4 are obtained to N-20 and comparative example is obtained respectively
Catalyst CN-1 to CN-4 carries out hydrodesulfurization reaction on miniature hydrogenation test apparatus by following step：By catalyst breakage
For the particle of 40-60 mesh, catalyst of the 1.5mL after broken is loaded into reactor flat-temperature zone, and fill out using the quartz sand of 40-60 mesh
Fill reactor two parts up and down.Reaction condition is as follows：230 DEG C, hydrogen dividing potential drop 1.6MPa, liquid hourly space velocity (LHSV) 8h of reaction temperature-1, hydrogen oil
Volume ratio 900, reaction raw materials are the n-heptane solution containing 2- methylthiophenes (0.48wt%) and n-hexylene (20wt%).Reaction
As a result row are shown in Table 1.The mass fraction of sulphur uses gas chromatograph (PONA posts, FID detections in product after reaction raw materials and hydrogenation
Device) measure.
The hydrodesulfurization activity (HDS) of catalyst is calculated by formula (1).
HDS=[(Sfeed-Sproduct)/SfeedThe formula of] × 100% (1)
SfeedAnd SproductThe mass fraction of reaction raw materials and 2- methylthiophenes in product after hydrogenation, % are represented respectively.
The catalyst hydrodesulfurization active of table 1
The hydrogenation that hydrogenation catalyst can be significantly improved using method provided by the invention it can be seen from the result of table 1 is taken off
Sulphur activity.And the catalyst seal of (passivation step is before or after activation step) stores after two months after transpassivation,
The hydrodesulfurization activity of catalyst illustrates that storage stability is good without being decreased obviously.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of method for improving hydrogenation catalyst desulfurization performance, this method includes successively being vulcanized the hydrogenation catalyst
And activation, the activation impregnate the hydrogenation catalyst after vulcanization including the use of the maceration extract containing organic oxygen-containing compound, then
It is heat-treated, wherein, the temperature of the heat treatment is 200-450 DEG C, and the time of heat treatment is 0.5-12 hours.
2. a kind of method pre-processed to hydrogenation catalyst, this method includes successively being vulcanized the hydrogenation catalyst
And activation, the activation impregnate the hydrogenation catalyst after vulcanization including the use of the maceration extract containing organic oxygen-containing compound, then
It is heat-treated, wherein, the temperature of the heat treatment is 200-450 DEG C, and the time of heat treatment is 0.5-12 hours.
3. method according to claim 1 or 2, wherein, on the basis of the total amount of the maceration extract, have in the maceration extract
The concentration of machine oxygenatedchemicals is 0.01-15wt%, and the concentration of organic oxygen-containing compound is 0.1- in preferably described maceration extract
4wt%.
4. according to the method described in any one in claim 1-3, wherein, the organic oxygen-containing compound be alcohol, ether, phenol and
At least one of acid；Preferably, the organic oxygen-containing compound be monohydric alcohol that carbon number is 2-10 and/or dihydric alcohol,
Carbon number is 2-10 monohydric phenol and/or dihydric phenol and their monoether and/or bis ether；It is further preferred that described have
Machine oxygenatedchemicals is in ethanol, ethylene glycol, isopropanol, propane diols, glycerine, butanol, butanediol, phenol, o-cresol
It is one or more.
5. according to the method described in any one in claim 1-4, wherein, the solvent of maceration extract be selected from water or petroleum ether,
One or more in normal heptane, n-decane, toluene, dimethylbenzene, petroleum ether, the distillate that boiling range is 40-360 DEG C.
6. according to the method described in any one in claim 1-5, wherein, the dipping impregnates for hole saturation.
7. according to the method described in any one in claim 1-6, wherein, the temperature of the heat treatment is 220-410 DEG C, heat
The time of processing is 1-10 hours；Preferably, the temperature of the heat treatment is 250-350 DEG C, and the time of heat treatment is small for 2-6
When.
8. according to the method described in any one in claim 1-7, wherein, the heat treatment is under inert gas shielding atmosphere
Carry out.
9. according to the method described in any one in claim 1-8, wherein, the mode of the vulcanization is to make hydrogen and vulcanization
The mixed gas of hydrogen is contacted with the hydrogenation catalyst.
10. the method according to claim 11, wherein, in the mixed gas of the hydrogen and hydrogen sulfide, hydrogen sulfide content
For 0.1-25 volume %, preferably 1-8 volumes %；The temperature of the vulcanization is 260-400 DEG C, and when the time is 1-48, pressure is
0.1-10 MPas, the volume space velocity 50-2000 hours of mixed gas-1；Preferably, the temperature of the vulcanization is 260-380 DEG C, pressure
Power is 0.1-5 MPas, and the time is 1-24 hours, and the volume space velocity of mixed gas is 100-1000 hours-1。
11. according to the method described in any one in claim 1-10, wherein, this method is additionally included in before activation and/or living
The hydrogenation catalyst after vulcanization is passivated after change, the mode of the passivation is by the hydrogenation catalyst after vulcanization and contains inertia
The mixed gas of G＆O contacts, and the content of oxygen is 0.05-10 in the mixed gas containing inert gas and oxygen
Volume %, preferably 0.1-5 volumes %.
12. according to the method for claim 11, wherein, the temperature of the passivation is room temperature to 100 DEG C, pressure 0.1-10
MPa, the time is 1-48 hours, the volume space velocity 50-2000 hours of mixed gas-1；It is preferred that the temperature being passivated is 30-70 DEG C, pressure
Power is 0.1-5 MPas, and the time is 1-12 hours, the volume space velocity 100-1000 hours of mixed gas-1。
13. according to the method described in any one in claim 1-12, wherein, the hydrogenation catalyst is urged selected from hydrofinishing
One kind in agent, hydrotreating catalyst and hydrocracking catalyst.
14. according to the method for claim 13, wherein, the hydrogenation catalyst contains carrier, organic complexing agent and extremely
A kind of less to be selected from group VIII and at least one metal component selected from vib, the metal of preferably described VIII is Co, the
The metal of group vib is Mo.
15. the method according to claim 11, wherein, on the basis of the total amount of the hydrogenation catalyst, organic network
The content of mixture is 5-30wt%, one or more of the organic complexing agent in organic carboxyl acid and its ammonium salt.
16. the pretreated hydrogenation catalyst obtained as the method described in any one in claim 2-15.
17. the hydrogenation catalyst described in method and/or claim 16 in claim 1-15 described in any one is being hydrogenated with
Application in desulphurization reaction.
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