CN106140322A - A kind of hydrogenation catalyst activation method and application thereof - Google Patents

Abstract

A kind of hydrogenation catalyst activation method and application thereof, said method comprising the steps of: hydrogenation catalyst, under the conditions of vulcanization reaction, is vulcanized by (1) with the material reaction containing sulfur-containing compound；(2) will be through the catalyst after step (1) vulcanizes and inert gas, one or more in nitrogen, argon, helium, carbon dioxide and water vapour of described noble gas, include with the condition of inert gas: pressure is that normal pressure is to 15 MPas；Temperature be room temperature to 400 DEG C, the time is 0.5-24 hour, and the volume space velocity of noble gas is 1-1500h^-1.Compared with prior art, the present invention provides the hydrodesulfurization activity of hydrogenation catalyst and stability to be improved.

Description

A kind of hydrogenation catalyst activation method and application thereof

Technical field

The present invention relates to a kind of hydrogenation catalyst and preparation method and applications.

Background technology

The environmental consciousness day by day strengthened and the strictest environmental regulation force oil refining circle more to focus on cleaning Fuel producing technology is developed, and how to have become oil refining circle current and modern for the production super-low sulfur oil product of economical rationality One of problem that emphasis solves is needed in the rear regular period.And develop and there is more high activity with the newest Type hydrogenation catalyst is then to produce one of most economical method of clear gusoline.

Summary of the invention

The technical problem to be solved in the present invention is to provide one and changes further by changing catalyst activation process The method of kind catalyst hydrogenation reactivity worth and the method application in hydrocarbon ils processing reaction.

The present invention relates to a kind of hydrogenation catalyst activation method, comprise the following steps: (1) is at vulcanization reaction Under the conditions of, by hydrogenation catalyst and the material reaction sulfuration containing sulfur-containing compound；(2) will be through step (1) catalyst after sulfuration and inert gas, described noble gas is selected from nitrogen, argon, helium One or more in gas, carbon dioxide and water vapour, include with the condition of inert gas: pressure For normal pressure to 15 MPa；Temperature be room temperature to 400 DEG C, the time is 0.5-24 hour, the body of noble gas Long-pending air speed is 1-1500h^-1。

Preferably, one or more in nitrogen, argon, helium of described noble gas, with inertia Gas contact condition include: pressure be normal pressure to 10 MPas, more preferably normal pressure is to 6 MPas； Temperature is 200-400 DEG C, more preferably 230-380 DEG C, and the time is 0.5-12 hour, the most excellent Electing as 1-8 hour, the volume space velocity of noble gas is 10-500h^-1, more preferably 10-300h^-1。

Preferably, the vulcanization reaction condition of described step (1) including: temperature 140-400 DEG C, and pressure is normal Pressing-15 MPas, the described material containing sulfur-containing compound is the gaseous mixture of hydrogen-containing gas and hydrogen sulfide, described In gaseous mixture, the volume fraction of hydrogen sulfide is 0.5-15%, and the volume space velocity of gaseous mixture is 100-3000h^-1； Or, the described material containing sulfur-containing compound is the mixture of sulfur-containing compound and hydrocarbon ils, described contains The mass fraction of the sulfur-containing compound counted with sulfur in the mixture of sulphur compound and hydrocarbon ils, as 0.1-15%, contains The liquid hourly space velocity (LHSV) of the mixture of sulphur compound and hydrocarbon ils is 0.1-20h^-1。

It is further preferred that the vulcanization reaction condition of described step (1) including: temperature 140-400 DEG C, Pressure normal pressure-10 MPas, the described material containing sulfur-containing compound is the mixing of hydrogen-containing gas and hydrogen sulfide Gas, in described gaseous mixture, the volume fraction of hydrogen sulfide is 3-10%, and the volume space velocity of gaseous mixture is 300- 1000h^-1；Or, the described material containing sulfur-containing compound is the mixing of sulfur-containing compound and hydrocarbon ils Thing, the mass fraction of the sulfur-containing compound counted with sulfur in the mixture of described sulfur-containing compound and hydrocarbon ils is as 1- 6%, the liquid hourly space velocity (LHSV) of the mixture of sulfur-containing compound and hydrocarbon ils is 1-5h^-1(h^-1For hour^-1)。

Wherein, described hydrocarbon ils is 30 DEG C of-350 DEG C of distillates selected from boiling range.

Described hydrogenation catalyst is selected from Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst Agent.It is especially selected from Hydrobon catalyst.

The method provided according to the present invention, is connecing the catalyst after step (1) vulcanizes with noble gas Including the step of displacement before Chuing, replacement media is 30 DEG C of-350 DEG C of fractions selected from hydrogen-containing gas and/or boiling range Oil, replace temperature 140-400 DEG C, displacement pressure be normal pressure to 15MPa MPa, time swap is 1-48 Hour.The most described displacement temperature is 140-360 DEG C, displacement pressure be normal pressure to 10 MPas, during displacement Between be 1-12 hour.

In the present invention, described hydrogen-containing gas refers to that hydrogen purity is 80%-100%, preferably 90%-100% Hydrogen-containing gas, for example, it may be hydrogen, hydrogen and methane and/or the gaseous mixture of ethane, volume space velocity is 1-1500h^-1, preferred volume air speed is 10-500h^-1, more preferably 10-300h^-1.Described boiling range is 30 DEG C of-350 DEG C of distillates can be selected from gasoline, boat coal, the distillate of diesel oil distillate, preferably wherein Direct steaming gasoline, the straight run boat distillate such as coal, straight-run diesel oil；Volume space velocity is 0.1-20h^-1, preferred volume Air speed is 1-5h^-1；Hydrogen is 100-3000, preferably 300-1000 with the volume ratio of described distillate.

The invention still further relates to preceding method application in hydrogenation reaction, particularly with hydrodesulfurization reaction For the application in main purpose hydrofining reaction.

Compared with existing catalyst, the catalyst that the present invention provides has higher hydrodesulfurization activity with steady Qualitative.

Such as, prepared by carrier prepared by the aluminium oxide shaping carrier provided by the present invention respectively and conventional method NiW hydrogenation catalyst C and DC (reference agent) that tenor is identical.It is former with catalytic cracking diesel oil Material, is evaluated the hydrodesulfurization activity of two kinds of catalyst.With the catalyst DC's after reacting 8 days Hydrodesulfurization activity is 100, and the hydrodesulfurization activity of catalyst C is 122.Result shows, with existing skill The catalyst that art provides carrier to prepare is compared, the present invention hydrodesulfurization providing carrier to prepare catalyst is lived Property and stability significantly improve.

Detailed description of the invention

In the present invention, before being enough to vulcanize hydrogenation catalyst with the material reaction containing sulfur-containing compound Putting, described vulcanization reaction can use arbitrary existing method to realize.

Be enough to make the catalyst after sulfuration under conditions of the present invention limits with described inert gas On the premise of reaction, arbitrary existing method can be used to realize this process, to this, the present invention does not has spy Do not limit.

According to the present invention, can directly proceed to step (2) after the sulfuration of described step (1) terminates Reaction, i.e. stops, into the material containing sulfur-containing compound, making the catalyst after sulfuration limit in the present invention Under the conditions of with inert gas haptoreaction；Can also be between described step (1) and step (2) Displacement (purging) step including a material containing sulfur-containing compound.Such as, sulfuration is adopted after terminating Purge with hydrogen and/or hydrocarbon ils, switch to noble gas afterwards and connect with noble gas of the present invention Haptoreaction under conditions of Chuing.Purging condition can be under the operation temperature of former vulcanization reaction, pressure condition Carry out, it is also possible to while purging, change the operating condition such as temperature, pressure, such as, adjust to step (2) operating condition etc. specified.

In the present invention, described hydrogenation catalyst can be arbitrarily with selected from group VIII base metal and Selected from the catalyst that vib metals is hydrogenation active metals component.For example, it may be hydrofinishing is urged Agent, hydrotreating catalyst, hydrocracking catalyst etc..It is especially suitable for hydrodesulfurization as mesh The activation of hydrogenation catalyst.In described catalyst selected from group VIII with selected from the metal of vib Component is conventional selection, and such as, described group VIII metal component is selected from cobalt and/or nickel, vib metals Component is selected from molybdenum and/or tungsten.

In a specific embodiment, on the basis of described catalyst, catalyst of the present invention preferably comprises With the group VIII metal component of 1-10 weight % that oxide (such as NiO, CoO) is counted, further preferably For 1.5-6 weight %, contain with oxide (such as MoO₃, WO₃) VIB of 5-40 weight % that counts Race's metal component, more preferably 10-35 weight %.They can be commercially available commodity or by arbitrarily Existing method prepare.Such as, Hydrobon catalyst disclosed in CN85104438, this catalyst is one Plant and use dipping, be dried catalyst prepared by the method for also roasting；Add disclosed in CN200910177170.6 Hydrogen catalyst for refining, this catalyst contains organic additive, uses prepared by dipping, drying means to urge for a kind of Agent etc..

In a particularly preferred embodiment, described hydrogenation catalyst is a kind of hydrofinishing catalysis Agent, described Hydrobon catalyst contains carrier and at least one is selected from at least one selected from group VIII The metal component of vib, described carrier is the boehmite of a kind of modification and/or false boehmite The gama-alumina obtained after molding, roasting.

The method of described modified boehmite and/or false boehmite includes: (1) is by least one oxygen Changing aluminum hydrate roasting, described roasting condition includes: temperature is 300 DEG C-950 DEG C, and the time is 0.5 little Time-24 hours；(2) product of roasting that step (1) is obtained and at least one boehmite and/or False boehmite and water mixing, obtain a kind of mixture；(3) mixing that step (2) is obtained Thing carries out hydrothermal treatment consists in closed reactor, and hydrothermal conditions includes: temperature is 60 DEG C-250 DEG C, Time is 0.5 hour-48 hours；(4) product that step (3) obtains is dried, obtains modification Boehmite and/or false boehmite.

Wherein, the roasting condition of preferred described step (1) including: temperature is 300-750 DEG C, the time For 1-24 hour.The roasting condition of further preferred described step (1) including: temperature is 350- 650 DEG C, the time is 2-10 hour.

The product of roasting that step (1) is obtained by the most described step (2) and at least one boehmite Or in the mixture that is mixed to get of false boehmite and water, solid content in mass is 1%-80%, Wherein, described product of roasting with the mass ratio of the boehmite in terms of butt or false boehmite is 0.1-20.Product of roasting that step (1) is obtained by further preferred described step (2) and at least one In the mixture that boehmite or false boehmite and water are mixed to get, solid content in mass For 5%-70%, wherein, described product of roasting and the boehmite in terms of butt or false boehmite Mass ratio is 0.2-12.

When the water content in described mixture be enough to make described mixture be serosity (such as, in mass Solid content be less than 35%) time, described step (4) be dried before preferably include filter step.

The hydrothermal conditions of preferred described step (3) including: temperature be 60 DEG C to less than 140 DEG C, the time is 0.5-48 hour.The hydrothermal conditions bag of further preferred described step (3) Including: temperature is 80-120 DEG C, the time is 4-24 hour.Or, preferred described step (3) Hydrothermal conditions includes: temperature is that the time is 0.5-more than or equal to 140 DEG C to less than or equal to 250 DEG C 48 hours；The hydrothermal conditions of further preferred described step (3) including: temperature is 150- 220 DEG C, the time is 4-24 hour.

The baking temperature of the most described step (4) is 60 DEG C-180 DEG C, and drying time is 0.5 hour-24 Hour.The baking temperature of further preferred described step (4) is 80 DEG C-150 DEG C, and drying time is 1 little Time-12 hours.

In the present invention, described hydrated alumina is selected from Alumina hydrate, false boehmite, a water One or more in softening aluminium stone.

Wherein, described Alumina hydrate includes gibbsite (α-Al₂O₃·3H₂O), surge aluminum stone (β₁- Al₂O₃·3H₂And promise diaspore (β O)₂-Al₂O₃·3H₂O)。

Described false boehmite is also called boehmite, characterizes with X-ray diffraction, for one at 14.5 ° There is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse in ± 0.5 ° (2 θ).

Described boehmite is also called boehmite, with X-ray diffraction characterize, for one 14.5 ° ± There is the hydrated alumina (of the strongest, narrow and sharp-pointed (020) crystallographic plane diffraction peak in 0.5 ° (2 θ) Boehmite 45.8 °, 51.6 ° and 55.2 ° occur respectively corresponding to (131), (220) and (151) diffraction maximum not available for false boehmite of crystal face).

Inventors of the present invention have surprisingly found that, by boehmite and/or false boehmite with a kind of or Several through 300 DEG C of-950 DEG C of roastings (heat treatment) 0.5-24 hour, preferably through 300 DEG C of-750 DEG C of roastings (heat treatment) 1-24 hour, further preferably through 350 DEG C of-650 DEG C of roastings (heat treatment) 2-10 hour Hydrated alumina and water mixing, obtain a kind of mixture, and by this mixture in hermetic container In 60 DEG C of-250 DEG C of hydrothermal treatment consists 0.5-48 hour, it is preferable over 80-220 DEG C of hydrothermal treatment consists 4-24 hour, Thus the relative crystallinity of the modified boehmite obtained and/or false boehmite improves, and thus warp The aluminium oxide that roasting obtains maintains higher specific surface area and pore volume.

In the present invention, when controlling hydrothermal treatment consists temperature and being more than 140 DEG C, gained modified product is a water Softening aluminium stone；When controlling hydrothermal treatment consists temperature less than 140 DEG C, the crystalline phase of products therefrom keeps with initiation material Unanimously.

In a detailed description of the invention, the crystalline phase preferably making described modified product is consistent with initiation material The hydrothermal conditions of described step (3) including: temperature be 60 DEG C to less than 140 DEG C, the time is 0.5-48 hour；The hydrothermal conditions of further preferred described step (3) including: temperature is 80-120 DEG C, the time is 1-24 hour.

In another embodiment, preferably making described modified product is the described of boehmite The hydrothermal conditions of step (3) including: temperature is more than or equal to 140 DEG C extremely less than or equal to 250 DEG C, Time is 0.5-48 hour；The hydrothermal conditions of further preferred described step (3) including: temperature Degree is for 150-220 DEG C, and the time is 4-24 hour.

In the present invention, described boehmite, false boehmite and gibbsite can be commercially available business Product, it is also possible to be to use arbitrary prior art to prepare, this is not particularly limited.

Be enough to described hydrated alumina 300 DEG C of-950 DEG C of roastings (heat treatment) 1-24 hour, Preferably through 300 DEG C of-750 DEG C of roastings (heat treatment) 1-24 hour, further preferably through 350 DEG C-650 DEG C Roasting (heat treatment) is under conditions of 2-10 hour, and the method for roasting described in step (1) is not had by the present invention There is restriction especially.For example, it may be by described hydrated alumina in usual baking oven or roaster Carry out roasting under air atmosphere, it is also possible to be in the baking oven or roaster of vacuum-pumping under vacuum Or be passed through under inert gas conditions and carry out.When described roasting is passed through noble gas, described noble gas can Be enough to arbitrarily to gasify under described roasting condition do not conform to carrier of oxygen, can be such as selected from nitrogen One or more in gas, argon, helium, carbon dioxide and water vapour.

Butt in the present invention refers to: a certain amount of described hydrated alumina Muffle furnace in air atmosphere In be raised to 600 DEG C with the heating rate of 4 DEG C/min, then 600 DEG C of constant temperature 4 hours, roasting afterproduct Weight and roasting before the percent of weight ratio of described hydrated alumina, butt=roasting afterproduct Weight × 100% of described hydrated alumina before the roasting of weight ÷.

In the present invention, described airtight reactor can be the reaction that can realize described hydro-thermal reaction arbitrarily Device, such as, autoclave etc., described reaction can be to carry out under static conditions, also at stirring shape Carry out under state, preferably under stirring, carry out hydrothermal treatment consists.

Described molding method be conventional method, such as methods such as tabletting, spin, extrusions.Adopting During with customary way molding, for guarantee molding be smoothed out introducing in aforesaid material to be formed help Agent is to allow, such as, when extrusion, can introduce appropriate peptizer in aforesaid material to be formed And/or extrusion aid and water, extrusion molding afterwards.Kind and the consumption of described extrusion aid may each be this area Conventional, the most common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyethylene One or more in alcohol, PVOH.

The aforesaid aluminium oxide of the present invention can be containing selected from silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, oxygen Change one or more adjuvant components in thorium, beryllium oxide, on the basis of described carrier, described adjuvant component Mass fraction be less than 10%, preferably 0.3%-5%.

When described carrier contains selected from silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, oxidation During one or more adjuvant components in beryllium, the preparation process at described carrier includes introducing selected from oxidation One or more adjuvant components in silicon, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide Step, the method for described introducing adjuvant component is conventional method.For example, it may be will contain selected from oxidation One or more adjuvant components in silicon, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide The mixture warp of one or more in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina Prepare after molding roasting.Can also be just aluminium oxide and/or its precursor and the chemical combination containing adjuvant component Thing mix, after obtain through molding, drying and roasting.

The aforesaid carrier of the present invention can contain clay and/or molecular sieve, on the basis of described carrier, institute The mass fraction stating clay and/or molecular sieve is less than 35%, preferably 1%-20%.

When in described carrier containing clay and/or molecular sieve, the preparation process at described carrier includes drawing Enter the step of clay and/or molecular sieve, the method thing conventional method of described introducing clay and/or molecular sieve.Example As, by fixed selected from Alumina hydrate, monohydrate alumina and nothing with described to described clay and/or molecular sieve The mixture of one or more in shape aluminium hydroxide prepares after molding roasting.

In the present invention, described clay can be selected from Kaolin, halloysite, montmorillonite, kieselguhr, One or many in galapectite, saponite, rectorite, meerschaum, attapulgite, brucite and bentonite Kind.Described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.Described zeolite molecular sieve is permissible For erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 Zeolite, ZSM-23 zeolite, ZSM-35 zeolite, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 Molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, One or more in ZSM-57 zeolite, faujasite, Beta zeolite and omega zeolite.Described nonzeolite Molecular sieve can be in phosphate aluminium molecular sieve, HTS and SAPO (that is, SAPO) molecular sieve One or more.According to the present invention, described molecular sieve is preferably hydrogen type molecular sieve.Described hydrogen type molecular sieve Can be commercially available, it would however also be possible to employ prepared by conventional method.For example, it is possible to by sodium form molecular sieve with often The ammonium ion exchange process of rule carries out ion exchange and is dried, and forms ammonium type molecular sieve, more fired formation hydrogen Type molecular sieve.

Arbitrary existing method can be used to introduce at least one group VIII and at least one in aforesaid carrier Plant vib metals component, for example, it may be will be containing at least one group VIII and at least one choosing The method impregnating described carrier after vib metals compound is configured to mixed solution；Can be to contain There are at least one group VIII and at least one leaching after vib metals compound individually prepares solution The method of stain carrier.Wherein, by the concentration of the solution to metallic components, consumption or carrier consumption Regulation and control, can prepare the described catalyst specifying content, and this is that those skilled in the art are held Intelligible.

Described group VIII metallic compound one or several in the soluble compound of these metals Kind, for example, it may be the nitrate of these metals, acetate, carbonate, chloride, solubility network One or more in compound.

Described vib metals compound one or several in the soluble compound of these metals Kind, for example, it may be in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate One or more.

In further preferred embodiment, possibly together with organic compound thing in described catalyst, such as Described organic compound is organic carboxyl acid and ammonium salt thereof, and described organic acid is selected from trans 1,2-hexamethylene two Amine tetraacethyl, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, acetaldehyde One or more in acid, hydroxyacetic acid, tartaric acid and malic acid and ammonium salt thereof, with catalyst as base Standard, the content of described organic compound is 1-20 weight %.

When in described catalyst possibly together with organic compound, arbitrary existing method can be used they to be drawn Enter catalyst, such as, use the method for dipping to introduce, such as, prepare with the mixture containing active metal mixed Close solution, introduce by the method for this solution impregnating carrier afterwards, or individually with containing described organic compound The method of the solution impregnating carrier of thing introduces.Described dipping is for preparing catalyst customary way, example As, can be spray process dipping, saturated dipping method and excess liquid dipping method.

After described impregnation steps completes, optionally can be dried, the step such as roasting or not roasting Suddenly.The described condition being dried with roasting is all conventional, and such as, baking temperature is 100-300 DEG C, preferably For 100-280 DEG C, drying time is 1-12 hour, preferably 2-8 hour；Sintering temperature is 350-550 DEG C, preferably 400-500 DEG C, roasting time is 1-10 hour, preferably 2-8 hour.

In the present invention, to described hydrocarbon oil hydrogenation reaction condition, there is no particular limitation, preferably reacts bar Part includes: reaction temperature 200-420 DEG C, more preferably 220-400 DEG C, pressure 2-18 MPa, More preferably 2-15 MPa, liquid hourly space velocity (LHSV) 0.3-10 hour^-1, more preferably 0.3-5 hour^{- 1}, hydrogen to oil volume ratio 50-5000, more preferably 50-4000.

The device of described hydrogenation reaction can any be enough to make described raw oil in hydrogenation conditions under with Described catalyst catalytic reaction dress device in carry out, such as, described reaction at fixed bed reactors, Moving-burden bed reactor or fluidized bed reactor are carried out.

The catalyst activation process that the present invention provides is suitable for oil, coal liquefaction fraction oil (such as, vapour Oil, boat coal, diesel oil etc.) hydrogenation process.

Detailed description of the invention

Example below will be further illustrated the present invention, but not thereby limiting the invention.

In following example, x-ray fluorescence method is used to be analyzed the content of element each in catalyst surveying It is fixed that (RIPP132-90, sees: Petrochemical Engineering Analysis method (RIPP test method), and Yang Cui is fixed Compile, Science Press, 1990,371-375).

The mensuration of sample crystalline phase, relative crystallinity and mean grain size is with reference to " solid catalyst Practical Research Method " (the big volume of Liu Weiqiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " petrochemical industry Analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying, Wu Wenhui compile, Science Press, 1990,394-405) the X-ray diffraction method in is carried out.

Modified boehmite that embodiment 1-10 declaratives carrier is used and/or false boehmite, Its preparation method and the alumina support thus prepared.

The hydrated alumina used in experiment is:

CL-A powder (false boehmite powder), relative relative crystallinity is 100%, grain size 2.9nm, butt 70 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.

CL-B powder (boehmite), relative relative crystallinity is 100%, grain size 5.2nm, Butt 78 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company).

CL-C powder (gibbsite (α-Al₂O₃·3H₂O)), relative relative crystallinity is 100%, Grain size 156nm, butt 65 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.

Wherein, weigh 10000 grams of CL-A powder, with banded extruder (manufacturer: section of South China Science & Engineering University Skill industry head factory, model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet Bar is dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain in air atmosphere Alumina support CL-A-Al₂O₃.Its crystalline phase, degree of crystallinity and crystal grain is characterized big by X-ray diffraction method Little, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result is listed in table In 2.

Weigh 10000 grams of CL-B powder, with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry is total Factory, model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar warp 120 DEG C were dried after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, are aoxidized in air atmosphere Alumina supporter CL-B-Al₂O₃.Its crystalline phase, degree of crystallinity and grain size is characterized by X-ray diffraction method, The results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result is listed in table 2 In.

According to the step in the method for modified boehmite of the present invention and/or false boehmite (1) product of roasting obtained is:

CL-A-600: weigh in 10000 grams of CL-A powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate is raised to 600 DEG C, and within 4 hours, obtains CL-A-600 at 600 DEG C of constant temperature.

CL-A-450: weigh in 10000 grams of CL-A powder Muffle furnaces in air atmosphere with 3 DEG C/min Heating rate is raised to 450 DEG C, and within 4 hours, obtains CL-A-450 at 450 DEG C of constant temperature.

CL-A-400: weigh in 10000 grams of CL-A powder Muffle furnaces in a nitrogen atmosphere with 5 DEG C/min Heating rate is raised to 400 DEG C, and within 4 hours, obtains CL-A-400 at 400 DEG C of constant temperature.

CL-A-350: weigh the liter with 3 DEG C/min in 10000 grams of CL-A powder baking ovens in a nitrogen atmosphere Temperature speed is raised to 350 DEG C, and within 4 hours, obtains CL-A-350 at 350 DEG C of constant temperature.

CL-B-600: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate is raised to 600 DEG C, and within 4 hours, obtains CL-B-600 at 600 DEG C of constant temperature.

CL-B-450: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate is raised to 450 DEG C, and within 4 hours, obtains CL-B-450 at 450 DEG C of constant temperature.

CL-B-400: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate is raised to 400 DEG C, and within 4 hours, obtains CL-B-400 at 400 DEG C of constant temperature.

CL-B-350: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate is raised to 350 DEG C, and within 4 hours, obtains CL-B-350 at 350 DEG C of constant temperature.

CL-C-600: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate be raised to 600 DEG C, and within 4 hours, obtain CL-C-600 at 600 DEG C of constant temperature.

CL-C-450: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate be raised to 450 DEG C, and within 6 hours, obtain CL-C-450 at 450 DEG C of constant temperature.

CL-C-400: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate be raised to 400 DEG C, and within 6 hours, obtain CL-C-400 at 400 DEG C of constant temperature.

CL-C-350: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere with 4 DEG C/min Heating rate be raised to 350 DEG C, and within 6 hours, obtain CL-C-350 at 350 DEG C of constant temperature.

Embodiment 1

Weigh 350 grams of CL-A powder in terms of butt, 120 grams of (CL-A-600 powder of CL-A-600 powder respectively It is 0.34 with the mass ratio of the powder of CL-A in terms of butt), they are mixed with 3600 grams of deionized waters and stirs Mix serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In pressure still, airtight post-heating to 160 DEG C, and under agitation constant temperature 4 hours；Afterwards, room temperature it is down to also After filtering, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S1 being modified.Penetrated by X- Line diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

By Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F- 26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S1 in air atmosphere.Pass through X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Logical Cross N₂Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.

Embodiment 2

Weigh 224 grams of CL-A powder in terms of butt, 300 grams of (CL-A-600 powder of CL-A-600 powder respectively It is 1.34 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters Stir into serosity；This serosity is transferred to the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In autoclave, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, by filter cake It is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S2 being modified.By X-ray diffraction side Method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S2.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.

Embodiment 3

Weigh 109 grams of CL-A powder in terms of butt, 464 grams of (CL-A-600 powder of CL-A-600 powder respectively It is 4.25 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters Stir into serosity；This serosity is transferred to the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In autoclave, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, by filter cake It is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S3 being modified.By X-ray diffraction side Method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S3.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.

Embodiment 4

Weigh 84 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, CL-A-400 powder respectively 150 grams, 250 grams of CL-A-450 powder, 180 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with The mass ratio of the CL-A powder in terms of butt is 8.10), they are mixed with 3600 grams of deionized waters and stirs Mix serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In pressure still, airtight post-heating to 160 DEG C constant temperature 4 hours；Be down to room temperature after filtering, by filter cake in 120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S4 being modified.By X-ray diffraction method Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S4 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S4.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.

Embodiment 5

Weigh 140 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, CL-A-400 powder respectively 200 grams, 300 grams of CL-A-450 powder, 10 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with The mass ratio of the CL-A powder in terms of butt is 4.36), they are mixed with 3100 grams of deionized waters and stirs Mix serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In pressure still, airtight post-heating to 60 DEG C constant temperature 48 hours；Be down to room temperature after filtering, by filter cake in 120 DEG C are dried 8 hours, obtain the hydrated alumina Q-S5 being modified.By X-ray diffraction method Characterizing its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S5 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S5.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.

Embodiment 6

Weigh 70 grams of CL-A powder in terms of butt, 200 grams of CL-A-350 powder, CL-A-400 powder respectively 100 grams, 400 grams of CL-A-450 powder, 20 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with The mass ratio of the CL-A powder in terms of butt is 10.29), they are mixed with 3200 grams of deionized waters Stir into serosity；This serosity is transferred to the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In autoclave, airtight post-heating to 100 DEG C constant temperature 24 hours；It is down to room temperature after filtering, by filter cake It is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S6 being modified.By X-ray diffraction side Method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S6 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S6.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.

Embodiment 7

Weigh 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, CL-A-350 powder 60 respectively Gram, 20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400 30 grams of powder, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, CL- 10 grams of C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder (total amount of CL-350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt), by they with 3600 grams of deionized waters are mixed into serosity；This serosity is transferred to band stirring volume be 5 liters not In the autoclave of rust steel band polytetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature And after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-being modified S7.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, result is listed in table In 1.

By Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F- 26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S7 in air atmosphere.Pass through X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Logical Cross N₂Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.

Embodiment 8

Weigh 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, CL-A-350 powder 60 respectively Gram, 20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400 30 grams of powder, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, CL- 10 grams of C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder (total amount of CL-350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt), by they with 3600 grams of deionized waters are mixed into serosity；This serosity is transferred to band stirring volume be 5 liters not In the autoclave of rust steel band polytetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours.It is down to room temperature After, high pressure kettle cover is opened, adds 11.75 grams of ammonium dihydrogen phosphates, continue stirring 24 hours in room temperature, After filtering, filter cake is dried 8 hours in 120 DEG C, obtains the aluminium oxide containing auxiliary agent phosphorus being modified Hydrate Q-S8.Its crystalline phase, relative crystallinity and grain size is characterized, knot by X-ray diffraction method Fruit is shown in Table 1.

By Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F- 26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S8 in air atmosphere.Pass through X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Logical Cross N₂Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.X-fluorescence method is used to measure The content of adjuvant component, the mass fraction of the described phosphate builder in terms of element is 0.41%.

Embodiment 9

Weigh 224 grams of CL-A powder in terms of butt, 300 grams of (CL-A-600 powder of CL-A-600 powder respectively It is 1.34 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters Stir into serosity；This serosity is transferred to the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In autoclave, airtight post-heating to 160 DEG C constant temperature 4 hours.After being down to room temperature, high pressure kettle cover is beaten Open, add 84.51 grams of titanium sulfates, continue stirring 24 hours, then filter.Filter cake is done through 120 DEG C Dry 8 hours, obtain the hydrated alumina Q-S9 containing auxiliary agent titanium being modified.Pass through X-ray diffraction Method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S9 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S9.Its crystalline phase, relative crystallinity and crystalline substance is characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, and result arranges In table 2.X-fluorescence method is used to measure the content of adjuvant component, the matter of the described titanium auxiliary agent in terms of element Amount mark is 3.12%.

Embodiment 10

Weigh 230 grams of CL-B powder in terms of butt, 320 grams of (CL-A-600 powder of CL-A-450 powder respectively It is 1.39 with the mass ratio of the powder of CL-B in terms of butt), they are mixed with 3600 grams of deionized waters and stirs Mix serosity；This serosity is transferred to the height of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In pressure still, airtight post-heating to 200 DEG C, and under agitation constant temperature 4 hours；Afterwards, room temperature it is down to also After filtering, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S10 being modified.Pass through X- Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.

By Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F- 26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is dried 4 hours through 120 DEG C After, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S10 in air atmosphere.Pass through X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Logical Cross N₂Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.

What the embodiment 11-13 explanation present invention used is prepared boehmite and/or vacation by conventional method of modifying The modifier of boehmite and the alumina support prepared by this modifier.

Embodiment 11

Weigh 470 grams of CL-A powder in terms of butt, by itself and 3600 grams of deionized water mix and blend pulpings Liquid；This serosity is transferred to the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, by filter cake in 120 DEG C It is dried 8 hours, obtains the hydrated alumina QBF-1 being modified.Characterized by X-ray diffraction method Its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.

QBF-1 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S11.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, result It is shown in Table 2.

Embodiment 12

Weigh 470 grams of CL-A-600 powder, itself and 3600 grams of deionized waters are mixed into serosity；Will In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity transfers to band stirring, airtight Post-heating was to 160 DEG C of constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 in 120 DEG C little Time, obtain the hydrated alumina QBF-2 being modified.By X-ray diffraction method characterize its crystalline phase, Relative crystallinity and grain size, the results are shown in Table 1.

QBF-2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S12.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, result It is shown in Table 2.

Embodiment 13

Weigh 470 grams of CL-B powder in terms of butt, by itself and 3600 grams of deionized water mix and blend pulpings Liquid；This serosity is transferred to the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring In, airtight post-heating to 200 DEG C constant temperature 4 hours；It is down to room temperature after filtering, by filter cake in 120 DEG C It is dried 8 hours, obtains the hydrated alumina QBF-3 being modified.Characterized by X-ray diffraction method Its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.

QBF-3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar.Wet bar is after 120 DEG C are dried 4 hours, and in Muffle furnace, 600 DEG C of constant temperature 4 are little in air atmosphere Time, obtain alumina support S13.By X-ray diffraction method characterize its crystalline phase, relative crystallinity and Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and pore volume, result It is shown in Table 2.

Table 1

Wherein, when measuring the degree of crystallinity of false boehmite, with CL-A powder as standard specimen；At the knot measuring boehmite When crystalline substance is spent, with CL-B powder as standard specimen；When measuring gama-alumina degree of crystallinity, with CL-B-Al₂O₃For standard specimen.

Table 2

Embodiment	Aluminium oxide	Specific surface area, m2/g	Pore volume, cm3/g
					CL-A-Al2O3	283	0.71
	CL-B-Al2O3	201	0.51
				1	S1	255	0.66
2	S2	238	0.62
				3	S3	213	0.61
4	S4	236	0.62
				5	S5	265	0.68
6	S6	258	0.66
				7	S7	216	0.60
8	S8	222	0.61
				9	S9	243	0.63
10	S10	185	0.60
				11	S11	233	0.52
12	S12	173	0.60
				13	S13	131	0.45

Embodiment 14 and 15 be described separately silicon oxide-containing alumina support and containing Y molecular sieve carrier and Preparation.

Embodiment 14

Preparation and the hydrated alumina Q-S2 powder of embodiment 2 equivalent, then with 25 grams of silicon dioxide powders With banded extruder (manufacturer: south China science and engineering is big after (purchased from middle petrochemical industry Chang Ling catalyst branch company) mixing Subject skill industry head factory, model: F-26 (III)) it is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters Bar, is dried 4 hours through 120 DEG C, the most in air atmosphere with the intensification speed of 4 DEG C/min in Muffle furnace Rate is raised to 600 DEG C, then 600 DEG C of constant temperature 4 hours, obtains alumina support S14.

Embodiment 15

Preparation and the hydrated alumina Q-S2 powder of embodiment 2 equivalent, then with 36 grams of Hydrogen Y molecules Sieve (Na₂O content 0.2%, cell parameter 2.464, relative crystallinity 88%, urge purchased from middle petrochemical industry Chang Ling Agent branch company) after mixing with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, type Number: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, is dried 4 through 120 DEG C little Time, the most in air atmosphere Muffle furnace is raised to 600 DEG C with the heating rate of 4 DEG C/min, then exists 600 DEG C of constant temperature 4 hours, obtains alumina support S15.

Embodiment 16-31 and the 32-41 explanation present invention use catalyst and preparation method thereof.

Embodiment 16-31

Respectively with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates, 3.18 grams of phosphoric acid (quality Mark 85%) and 16.66 grams of Fructus Citri Limoniae aqueous acids 199 milliliters dipping embodiments 1-15 prepare S1、S2、S3、S4、S5、S6、S7、S8、S9、S10、S11、S12、S13、S14、S15 And CL-A-Al₂O₃, dip time 2 hours, impregnation product is dried 4 hours in 120 DEG C afterwards, To catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, (carrier is CL-A-Al for C13, C14, C15 and C16₂O₃)。

Embodiment 32

Weigh carrier S 11 200 grams, by this carrier S 11 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours, obtain catalyst C17.

Embodiment 33

Weigh carrier S 12 200 grams, by this carrier S 12 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours, obtain catalyst C18.

Embodiment 34

Weigh carrier S 13 200 grams, by this carrier S 13 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours, obtain catalyst C19.

Embodiment 35

Weigh support C L-A-Al₂O₃200 grams, by this support C L-A-Al₂O₃With containing 63.46 grams of metatungstic acids Ammonium, the aqueous solution 199 milliliters of 23.45 grams of Nickelous nitrate hexahydrates impregnate above-mentioned carrier 2 hours, then exist 120 DEG C are dried 4 hours, and 420 DEG C of roastings 4 hours obtain catalyst C20.

Embodiment 36

Weigh carrier S 1 200 grams, by this carrier S 1 with containing 63.46 grams of ammonium metatungstates, 23.45 gram of six water The aqueous solution 199 milliliters closing nickel nitrate impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, 420 DEG C of roastings 4 hours, obtain catalyst C21.

Embodiment 37

Weigh carrier S 11 200 grams, by this carrier S 11 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours；Again with the ammonia spirit containing 22.27 grams of ethylenediaminetetraacetic acid 189 milliliters leaching The above-mentioned carrier of stain 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst C22.

Embodiment 38

Weigh carrier S 12 200 grams, by this carrier S 12 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours；Again with the ammonia spirit containing 22.27 grams of ethylenediaminetetraacetic acid 189 milliliters leaching The above-mentioned carrier of stain 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst C23.

Embodiment 39

Weigh carrier S 13 200 grams, by this carrier S 13 with containing 63.46 grams of ammonium metatungstates, 23.45 gram six The aqueous solution of nitric hydrate nickel 199 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 at 120 DEG C little Time, 420 DEG C of roastings 4 hours；Again with the ammonia spirit containing 22.27 grams of ethylenediaminetetraacetic acid 189 milliliters leaching The above-mentioned carrier of stain 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst C24.

Embodiment 40

Weigh support C L-A-Al₂O₃200 grams, by this support C L-A-Al₂O₃With containing 63.46 grams of metatungstic acids Ammonium, the aqueous solution 199 milliliters of 23.45 grams of Nickelous nitrate hexahydrates impregnate above-mentioned carrier 2 hours, then exist 120 DEG C are dried 4 hours, 420 DEG C of roastings 4 hours；Molten with the ammonia containing 22.27 grams of ethylenediaminetetraacetic acid again Liquid 189 milliliters impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, obtains catalyst C25。

Embodiment 41

Weigh carrier S 1 200 grams, by this carrier S 1 with containing 63.46 grams of ammonium metatungstates, 23.45 gram of six water The aqueous solution 199 milliliters closing nickel nitrate impregnates above-mentioned carrier 2 hours, is then dried 4 hours at 120 DEG C, 420 DEG C of roastings 4 hours；Again with on the ammonia spirit containing 22.27 grams of ethylenediaminetetraacetic acid 189 milliliters dipping State carrier 2 hours, be then dried 4 hours at 120 DEG C, obtain catalyst C26.

Catalyst performance evaluation:

Evaluate the explanation of comparative example 1-26 and conventionally carry out catalyst vulcanization and effect thereof.

Catalyst is C1-C26.

Reaction is carried out in 30 milliliters of fixed bed reactors, and catalyst particle size is 20～30 mesh, and catalyst is used Amount is 30ml.

Catalyst vulcanization, sulfurized oil is the straight run boat coal containing 2% Carbon bisulfide, and vulcanization reaction condition includes: Temperature 320 DEG C, sulfurized oil volume space velocity 2h^-1Charging；Pressure 6.4MPa；Hydrogen to oil volume ratio 300, time Between 8 hours.

It is 360 DEG C that sulfuration adjusts reaction temperature after terminating, and is passed through catalytic cracking diesel oil raw oil (sulfur content 11000 μ g/g, nitrogen content 1289 μ g/g, total arene content 69 weight %, polycyclic aromatic hydrocarbon content 39 weight %) reacting, concrete reaction condition includes: pressure 6.4MPa, and reaction temperature is 360 DEG C, body of feedstock Long-pending air speed 2h^-1；Hydrogen to oil volume ratio 300.

Experiment uses off-line sampling to carry out the sulfur content in assay products, in stable reaction 1 day (24 hours) After start sampling, then took a sample every 1 day, reaction continues 8 days.The sample obtained is with using microcoulomb Logical sequence sulphur content determination instrument is analyzed.Result is listed in table 3.

Evaluate the embodiment 1-26 explanation present invention and method and effect thereof are provided.

Catalyst is C1-C26.

Reaction is carried out in 30 milliliters of fixed bed reactors, and catalyst particle size is 20～30 mesh, and catalyst is used Amount is 30ml.

Method is provided to carry out activation of catalyst according to the present invention:

Step (1): catalyst vulcanization, sulfurized oil is the straight run boat coal containing 2% Carbon bisulfide, and sulfuration is anti- Condition is answered to include: temperature 320 DEG C, sulfurized oil volume space velocity 2h^-1Charging；Pressure 6.4MPa；Hydrogen oil body Long-pending ratio 300,8 hours time.

Step (2): sulfuration purges after terminating, adjusts operating condition to step in purge (2) condition needed for.Wherein, blowing medium is listed in table 3.Afterwards, noble gas, noble gas are introduced And haptoreaction condition is listed in table 3.Experiment uses hydrogen and straight-run diesel oil (sulfur content 9800 μ g/g, Nitrogen content 120 μ g/g, total arene content 31 weight %, polycyclic aromatic hydrocarbon content 12 weight %) it is situated between for purging Matter.

Hydrogenation reaction: it is 6.4MPa that nitrogen switches to hydrogen, adjustment pressure；Reaction temperature is 360 ℃；Hydrogen to oil volume ratio 300, by volume air speed 2h in reactor^-1(sulfur contains to introduce catalytic cracking diesel oil Measure 11000 μ g/g, nitrogen content 1289 μ g/g, total arene content 69 weight %, polycyclic aromatic hydrocarbon content 39 weight Amount %) reaction oil, reacts.

Experiment uses off-line sampling to carry out the sulfur content in assay products, in stable reaction 1 day (24 hours) After start sampling, then took a sample every 1 day, reaction continues 8 days.The sample obtained is with using microcoulomb Logical sequence sulphur content determination instrument is analyzed.Wherein, hydrodesulfurization activity A is calculated as follows:

A=ln [100/ (100-X)], in formula, the desulfurization degree that X is.

Taking the hydrodesulfurization activity that catalyst C22 conventionally vulcanizes is 100, then other catalyst Relative hydrodesulfurization activity can be represented by the formula:

Relative activity=(A_QT/A_C22) × 100%, A in formula_QTFor the activity of other catalyst, A_C22For urging The activity of agent C22.Result is listed in table 3.

Table 3

Being shown by the result of table 3, the present invention provides method to have higher hydrodesulfurization activity and stability.

Claims (10)

1. a hydrogenation catalyst activation method, comprises the following steps: (1) under the conditions of vulcanization reaction, By hydrogenation catalyst and the material reaction sulfuration containing sulfur-containing compound；(2) will be after step (1) vulcanizes Catalyst and inert gas, described noble gas be selected from nitrogen, argon, helium, carbon dioxide With one or more in water vapour, include with the condition of inert gas: pressure is that normal pressure is to 15,000,000 Handkerchief；Temperature be room temperature to 400 DEG C, the time is 0.5-24 hour, and the volume space velocity of noble gas is 1- 1500h^-1。

Method the most according to claim 1, it is characterised in that described noble gas selected from nitrogen, One or more in argon, helium, include with the condition of inert gas: pressure is that normal pressure is to 10 MPa, more preferably normal pressure is to 6 MPas；Temperature is 200-400 DEG C, more preferably 230- 380 DEG C, the time is 0.5-12 hour, more preferably 1-8 hour, and the volume space velocity of noble gas is 10-500h^-1, more preferably 10-300h^-1。

Method the most according to claim 1, it is characterised in that the vulcanization reaction of described step (1) Condition includes: temperature 140-400 DEG C, pressure normal pressure-15 MPas, the described material containing sulfur-containing compound For hydrogen-containing gas and the gaseous mixture of hydrogen sulfide, in described gaseous mixture, the volume fraction of hydrogen sulfide is 0.5- 15%, the volume space velocity of gaseous mixture is 100-3000h^-1；Or, the described thing containing sulfur-containing compound Material is sulfur-containing compound and the mixture of hydrocarbon ils, in the mixture of described sulfur-containing compound and hydrocarbon ils in terms of sulfur The liquid space-time of the mixture that mass fraction is 0.1-15%, sulfur-containing compound and hydrocarbon ils of sulfur-containing compound Speed is 0.1-20h^-1。

Method the most according to claim 3, it is characterised in that the vulcanization reaction of described step (1) Condition includes: temperature 140-400 DEG C, pressure normal pressure-10 MPas, the described material containing sulfur-containing compound For hydrogen-containing gas and the gaseous mixture of hydrogen sulfide, in described gaseous mixture, the volume fraction of hydrogen sulfide is 3-10%, The volume space velocity of gaseous mixture is 300-1000h^-1；Or, the described material containing sulfur-containing compound is for containing Sulphur compound and the mixture of hydrocarbon ils, sulfur-bearing in terms of sulfur in the mixture of described sulfur-containing compound and hydrocarbon ils The mass fraction of compound be the liquid hourly space velocity (LHSV) of the mixture of 1-6%, sulfur-containing compound and hydrocarbon ils be 1-5h^{- 1}。

5. according to the method described in claim 3 or 4, it is characterised in that described hydrocarbon ils selected from boiling range is 30 DEG C of-350 DEG C of distillates.

Method the most according to claim 1, it is characterised in that described hydrogenation catalyst is selected from hydrogenation Catalyst for refining, hydrotreating catalyst, hydrocracking catalyst.

Method the most according to claim 6, it is characterised in that described hydrogenation catalyst is hydrogenation essence Catalyst processed.

Method the most according to claim 1, it is characterised in that will through step (1) vulcanize after Including the step of displacement before catalyst and inert gas, replacement media is selected from hydrogen-containing gas and/or boiling range Be 30 DEG C of-350 DEG C of distillates, replace temperature 140-400 DEG C, displacement pressure be normal pressure to 15 MPas, put The time of changing is 1-48 hour.

Method the most according to claim 8, it is characterised in that described displacement temperature is 140-360 DEG C, displacement pressure be normal pressure to 10 MPas, time swap is 1-12 hour.

10. according to the application in hydrogenation reaction of the method described in claim 1-9.