CN106140322B - A kind of hydrogenation catalyst activation method and its application - Google Patents
A kind of hydrogenation catalyst activation method and its application Download PDFInfo
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Abstract
A kind of hydrogenation catalyst activation method and its application, the described method comprises the following steps: (1) under the conditions of vulcanization reaction, hydrogenation catalyst and the material reaction containing sulfur-containing compound being vulcanized；(2) by catalyst and inert gas after step (1) vulcanizes, the inert gas is selected from one or more of nitrogen, argon gas, helium, carbon dioxide and water vapour, and the condition with inert gas includes: that pressure is normal pressure to 15 megapascal；Temperature is room temperature to 400 DEG C, and the time is 0.5-24 hours, and the volume space velocity of inert gas is 1-1500h‑1.Compared with prior art, the present invention provides the hydrodesulfurization activity of hydrogenation catalyst and stability and is improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method and applications.
Background technique
It is raw that the environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter force oil refining circle more to focus on clean fuel
Technological development is produced, how the production super-low sulfur oil product of economical rationality, which has become, needs weight in oil refining circle's current and expected future regular period
One of the project that point solves.And developing the novel hydrogenation catalyst with more high activity and selectivity then is to produce clear gusoline most
Economic one of method.
Summary of the invention
The technical problem to be solved in the present invention is to provide one kind further to improve catalysis by changing catalyst activation process
Application of the method and this method of agent hydrogenation reaction performance in hydrocarbon ils processing reaction.
The present invention relates to a kind of hydrogenation catalyst activation methods, comprising the following steps: (1), will under the conditions of vulcanization reaction
Hydrogenation catalyst vulcanizes with the material reaction containing sulfur-containing compound；(2) by catalyst and indifferent gas after step (1) vulcanizes
Body contact, the inert gas is selected from one or more of nitrogen, argon gas, helium, carbon dioxide and water vapour, with indifferent gas
The condition of body contact includes: that pressure is normal pressure to 15 megapascal；Temperature is room temperature to 400 DEG C, and the time is 0.5-24 hours, indifferent gas
The volume space velocity of body is 1-1500h-1。
Preferably, the inert gas is selected from one or more of nitrogen, argon gas, helium, with inert gas
Condition includes: that pressure is normal pressure to 10 megapascal, further preferably normal pressure to 6 megapascal；Temperature is 200-400 DEG C, further excellent
It is selected as 230-380 DEG C, the time is 0.5-12 hours, and further preferably 1-8 hours, the volume space velocity of inert gas was 10-
500h-1, further preferably 10-300h-1。
Preferably, the vulcanization reaction condition of the step (1) includes: 140-400 DEG C of temperature, -15 megapascal of pressure normal pressure, institute
The gaseous mixture that the material containing sulfur-containing compound is hydrogen-containing gas and hydrogen sulfide is stated, the volume fraction of hydrogen sulfide in the gaseous mixture
For 0.5-15%, the volume space velocity of gaseous mixture is 100-3000h-1；Either, the material containing sulfur-containing compound is sulfur-bearing
The quality of sulfur-containing compound in the mixture of the mixture of compound and hydrocarbon ils, the sulfur-containing compound and hydrocarbon ils in terms of sulphur point
Counting is 0.1-15%, and the liquid hourly space velocity (LHSV) of the mixture of sulfur-containing compound and hydrocarbon ils is 0.1-20h-1。
It is further preferred that the vulcanization reaction condition of the step (1) includes: 140-400 DEG C of temperature, pressure normal pressure -10
Megapascal, the material containing sulfur-containing compound are the gaseous mixture of hydrogen-containing gas and hydrogen sulfide, hydrogen sulfide in the gaseous mixture
Volume fraction is 3-10%, and the volume space velocity of gaseous mixture is 300-1000h-1；Either, the material containing sulfur-containing compound
For the mixture of sulfur-containing compound and hydrocarbon ils, sulfur-containing compound in the mixture of the sulfur-containing compound and hydrocarbon ils in terms of sulphur
Mass fraction is 1-6%, and 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, it is 30 DEG C of -350 DEG C of distillates that the hydrocarbon ils, which is selected from boiling range,.
The hydrogenation catalyst is selected from Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst.Especially
Selected from Hydrobon catalyst.
According to the method provided by the invention, include before by the catalyst and inert gas after step (1) vulcanization
The step of displacement, replacement media is selected from hydrogen-containing gas and/or boiling range is 30 DEG C of -350 DEG C of distillates, replaces 140-400 DEG C of temperature,
Replacing pressure is normal pressure to 15MPa megapascal, and time swap is 1-48 hours.It is preferred that the displacement temperature is 140-360 DEG C, displacement
Pressure is normal pressure to 10 megapascal, and time swap is 1-12 hours.
In the present invention, the hydrogen-containing gas refers to that hydrogen purity is 80%-100%, preferably 90%-100% hydrogen
Body, for example, it may be the gaseous mixture of hydrogen, hydrogen and methane and/or ethane, volume space velocity 1-1500h-1, preferred volume sky
Speed is 10-500h-1, further preferably 10-300h-1.The boiling range be 30 DEG C of -350 DEG C of distillates can be selected from gasoline,
The distillate of boat coal, diesel oil distillate, the distillates such as direct steaming gasoline, straight run boat coal, straight-run diesel oil preferably wherein；Volume space velocity is
0.1-20h-1, preferred volume air speed is 1-5h-1；The volume ratio of hydrogen and the distillate is 100-3000, preferably 300-
1000。
The application that the invention further relates to preceding methods in hydrogenation reaction, especially with hydrodesulfurization reaction be main syllabus
Hydrofining reaction in application.
Compared with existing catalyst, catalyst provided by the invention has higher hydrodesulfurization activity and stability.
For example, preparing tenor with carrier prepared by aluminium oxide shaping carrier provided by the invention and conventional method respectively
Identical NiW hydrogenation catalyst C and DC (reference agent).Hydrodesulfurization using catalytic cracking diesel oil as raw material, to two kinds of catalyst
Activity is evaluated.With the hydrodesulfurization activity of the catalyst DC after reaction 8 days for 100, the hydrodesulfurization activity of catalyst C is
122.The result shows that providing carrier compared with the prior art provides the catalyst of carrier preparation by the present invention and preparing catalyst
Hydrodesulfurization activity and stability significantly improve.
Specific embodiment
In the present invention, under the premise of being enough to vulcanize hydrogenation catalyst with the material reaction containing sulfur-containing compound, institute
The vulcanization reaction stated can be used arbitrary existing method and realize.
It is reacted under conditions of being enough to make the catalyst after vulcanizing in present invention restriction with the inert gas
Under the premise of, arbitrary existing method can be used and realize this process, in this regard, the present invention is not particularly limited.
According to the present invention, it can directly be transferred to the reaction of step (2) after the vulcanization of the step (1), that is, stop
Into the material containing sulfur-containing compound, the catalyst after making vulcanization is contacted under conditions of the present invention limits with inert gas
Reaction；It can also include the displacement (purging) of a material containing sulfur-containing compound between the step (1) and step (2)
Step.For example, purging after vulcanization using hydrogen and/or hydrocarbon ils, it is switched to inert gas later and of the present invention
With haptoreaction under conditions of inert gas.Purging condition can be under the operation temperature of former vulcanization reaction, pressure condition
It carries out, the operating conditions such as temperature, pressure can also be changed while purging, such as adjust the operation item specified to step (2)
Part etc..
In the present invention, the hydrogenation catalyst can be arbitrary with the base metal selected from group VIII and selected from the
Group vib metal is the catalyst of hydrogenation active metal component.For example, it may be Hydrobon catalyst, hydrotreating catalyst,
Hydrocracking catalyst etc..It is especially suitable for using hydrodesulfurization as the activation of purpose hydrogenation catalyst.In the catalyst
Metal component selected from group VIII and selected from group VIB is conventional selection, for example, the group VIII metal component is selected from cobalt
And/or nickel, vib metals group are selected from molybdenum and/or tungsten.
In a specific embodiment, on the basis of the catalyst, catalyst of the present invention is preferably comprised with oxide
The group VIII metal component of the 1-10 weight % of (such as NiO, CoO) meter, further preferably 1.5-6 weight %, containing with oxygen
Compound (such as MoO3, WO3) meter 5-40 weight % vib metals component, further preferably 10-35 weight %.They can
To be commercially available commodity or be prepared by arbitrary existing method.For example, Hydrobon catalyst disclosed in CN85104438, this is urged
Agent is a kind of using the catalyst impregnated, prepared by method that is dry and roasting；CN200910177170.6 is disclosed plus hydrogen is smart
Catalyst processed, the catalyst contain organic additive, to be a kind of using dipping, catalyst of drying means preparation etc..
In a particularly preferred embodiment, the hydrogenation catalyst is a kind of Hydrobon catalyst, described to add
Hydrogen catalyst for refining contains carrier and at least one selected from group VIII and at least one metal component selected from group VIB, institute
State a kind of boehmite that carrier is modification and/or obtained gama-alumina after false boehmite is formed, roasted.
The method of the modified boehmite and/or false boehmite includes: (1) by least one alumina hydration
Object roasting, the roasting condition include: that temperature is 300 DEG C -950 DEG C, and the time is -24 hours 0.5 hour；(2) step (1) is obtained
The product of roasting arrived is mixed at least one boehmite and/or false boehmite and water, obtains a kind of mixture；
(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include: that temperature is 60
DEG C -250 DEG C, the time is -48 hours 0.5 hour；(4) product for obtaining step (3) is dry, obtains modified boehmite
And/or false boehmite.
Wherein, it is 300-750 DEG C that the roasting condition of the preferred step (1), which includes: temperature, and the time is 1-24 hours.
The roasting condition of the further preferred step (1) includes: that temperature is 350-650 DEG C, and the time is 2-10 hours.
It is preferred that the product of roasting and at least one boehmite or a false water that the step (2) obtains step (1) are soft
In the mixture that aluminium stone and water are mixed to get, solid content in mass is 1%-80%, wherein the product of roasting with
The mass ratio of the boehmite of butt meter or false boehmite is 0.1-20.The further preferred step (2) is by step
(1) in the mixture that the product of roasting and at least one boehmite or false boehmite and water obtained is mixed to get,
Solid content in mass be 5%-70%, wherein the product of roasting in terms of butt boehmite or vacation one water it is soft
The mass ratio of aluminium stone is 0.2-12.
When the water content in the mixture is enough to make the mixture slurries (for example, solid content in mass
It is 35% or less) when, the step of filtering is preferably included before the drying of the step (4).
The hydrothermal conditions of the preferred step (3) include: that temperature is 60 DEG C to less than 140 DEG C, time 0.5-
48 hours.The hydrothermal conditions of the further preferred step (3) include: that temperature is 80-120 DEG C, and the time is that 4-24 is small
When.Either, it is more than or equal to 140 DEG C to less than to be equal to that the hydrothermal conditions of the preferred step (3), which include: temperature,
250 DEG C, the time is 0.5-48 hours；The hydrothermal conditions of the further preferred step (3) include: that temperature is 150-
220 DEG C, the time is 4-24 hours.
It is preferred that the drying temperature of the step (4) is 60 DEG C -180 DEG C, drying time is -24 hours 0.5 hour.Further
It is preferred that the drying temperature of the step (4) is 80 DEG C -150 DEG C, drying time is -12 hours 1 hour.
In the present invention, the hydrated alumina is in hibbsite, false boehmite, boehmite
It is one or more of.
Wherein, the hibbsite includes gibbsite (α-Al2O3·3H2O), surge aluminium stone (β1-Al2O3·3H2O)
With promise diaspore (β2-Al2O3·3H2O)。
The vacation boehmite is also known as boehmite, is one kind at 14.5 ° ± 0.5 ° (2 with X-ray diffraction characterization
θ) there is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse.
The boehmite is also known as boehmite, with X-ray diffraction characterization, goes out to be a kind of at 14.5 ° ± 0.5 ° (2 θ)
Existing strongest, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and
55.2 ° occur corresponding to diffraction maximum not available for the false boehmite of (131), (220) and (151) crystal face respectively).
Inventors of the present invention have surprisingly found that by boehmite and/or false boehmite and one or more of warps
300 DEG C -950 DEG C of roastings (heat treatment) 0.5-24 hours, preferably through 300 DEG C -750 DEG C of roastings (heat treatment) 1-24 hours, into one
The hydrated alumina and water that step preferably roasts (heat treatment) 2-10 hours through 350 DEG C -650 DEG C mix, and obtain a kind of mixing
Object, and by the mixture in closed container in 60 DEG C -250 DEG C of hydro-thermal process 0.5-48 hours, be preferable over 80-220 DEG C of hydro-thermal
Processing 4-24 hours, thus the relative crystallinity of modified obtained boehmite and/or false boehmite improves, and thus
The aluminium oxide being fired maintains higher specific surface area and Kong Rong.
In the present invention, when controlling hydro-thermal process temperature is 140 DEG C or more, gained modified product is boehmite；Control
When hydro-thermal process temperature processed is less than 140 DEG C, crystal phase and the starting material of products therefrom are consistent.
In a specific embodiment, preferably make the crystal phase of the modified product and the consistent step of starting material
Suddenly it is 60 DEG C to less than 140 DEG C that the hydrothermal conditions of (3), which include: temperature, and the time is 0.5-48 hours；Further preferred institute
It is 80-120 DEG C that the hydrothermal conditions for stating step (3), which include: temperature, and the time is 1-24 hours.
In another embodiment, preferably make the step (3) of the modified product boehmite
Hydrothermal conditions include: temperature be more than or equal to 140 DEG C to less than be equal to 250 DEG C, the time be 0.5-48 hours；Further
The hydrothermal conditions of the preferred step (3) include: that temperature is 150-220 DEG C, and the time is 4-24 hours.
In the present invention, the boehmite, false boehmite and gibbsite can be commercially available commodity, can also be with
It is that this is not particularly limited using arbitrary prior art preparation.
Be enough by the hydrated alumina 300 DEG C -950 DEG C of roastings (heat treatment) 1-24 hours, preferably through 300
DEG C -750 DEG C roasting (heat treatment) 1-24 hours, the item further preferably through 350 DEG C of -650 DEG C of roastings (heat treatment) 2-10 hours
Under part, method of roasting described in step (1) is not particularly limited in the present invention.For example, it may be by the hydrated alumina
It is roasted, is also possible in the baking oven or roaster of vacuum-pumping under air atmosphere in usual baking oven or roaster
Under vacuum conditions or it is passed through under inert gas conditions and carries out.When the roasting is passed through inert gas, the inert gas can
To be arbitrary the carrier of oxygen that do not conform to for being enough to gasify under the roasting condition, for example, can be selected from nitrogen, argon gas, helium,
One or more of carbon dioxide and water vapour.
Butt in the present invention refers to: a certain amount of hydrated alumina in air atmosphere in Muffle furnace with 4 DEG C/
Minute heating rate be raised to 600 DEG C, then 600 DEG C constant temperature 4 hours, after roasting the weight of product and roast before the oxidation
The percentage of the weight ratio of aluminium hydrate, the weight of the hydrated alumina before the weight ÷ of product is roasted after butt=roasting
Amount × 100%.
In the present invention, the closed reactor can be arbitrary the reactor that the hydro-thermal reaction can be achieved, for example,
Autoclave etc., the reaction can be to be carried out under static conditions, is also carried out under stirring, preferably under stirring
Carry out hydro-thermal process.
The molding method is conventional method, such as the methods of tabletting, spin, extrusion.Using usual side
When method forms, to ensure that molding go on smoothly introduces auxiliary agent into material to be formed above-mentioned and be allowed, such as work as extrusion
When, suitable peptizing agent and/or extrusion aid and water can be introduced into material to be formed above-mentioned, extrusion molding later.It is described
The type and dosage of extrusion aid may each be this field routine, such as common extrusion aid can be fine selected from sesbania powder, methyl
Tie up one or more of element, starch, polyvinyl alcohol, polyethanol.
Present invention aluminium oxide above-mentioned can be containing selected from silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, oxidation
One or more of beryllium adjuvant component, on the basis of the carrier, the mass fraction of the adjuvant component is 10% hereinafter, excellent
It is selected as 0.3%-5%.
One of silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide are selected from when containing in the carrier
It include introducing to be selected from silica, titanium oxide, magnesia, oxidation in the preparation process of the carrier or when several adjuvant components
The step of one or more of zirconium, thorium oxide, beryllium oxide adjuvant component, the method for introducing adjuvant component are routine side
Method.For example, it may be will contain selected from one or more of silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide
The mixture of one or more of hibbsite, monohydrate alumina and the amorphous hydroted alumina of adjuvant component through at
It is made after type and roasting.Be also possible to aluminium oxide and/or its precursor will be mixed with the compound containing adjuvant component, after pass through
Molding, drying and roasting obtain.
Clay and/or molecular sieve, on the basis of the carrier, the clay can be contained in present invention carrier above-mentioned
And/or the mass fraction of molecular sieve is 35% hereinafter, preferably 1%-20%.
It include introducing clay in the preparation process of the carrier when containing clay and/or molecular sieve in the carrier
And/or the step of molecular sieve, the method object conventional method for introducing clay and/or molecular sieve.For example, by the clay and/
Or molecular sieve is selected from the mixed of one or more of hibbsite, monohydrate alumina and amorphous hydroted alumina with described
Object is closed to be made after molding and roasting.
In the present invention, the clay can selected from kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite,
One of rectorite, sepiolite, attapulgite, hydrotalcite and bentonite are a variety of.The molecular sieve can be zeolite molecules
Sieve and/or non-zeolite molecular sieve.The zeolite molecular sieve can 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 molecule
Sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta
One of zeolite and omega zeolite are a variety of.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, Titanium Sieve Molecular Sieve and phosphoric acid
One of sial (that is, SAPO) molecular sieve is a variety of.According to the present invention, the molecular sieve is preferably hydrogen type molecular sieve.It is described
Hydrogen type molecular sieve can be commercially available, can also be using conventional method preparation.For example, can be conventional by sodium form molecular sieve
Ammonium ion exchange process carries out ion exchange and drying, forms ammonium type molecular sieve, then be fired and to form hydrogen type molecular sieve.
Arbitrary existing method can be used and introduce at least one group VIII and at least one Section VI B into carrier above-mentioned
Race's metal component, for example, it may be will match containing at least one group VIII and at least one vib metals compound that is selected from
The method that the carrier is impregnated after mixed solution is made；Can be will be containing at least one group VIII and at least one selected from the
The method that group vib metallic compound individually prepares impregnated carrier after solution.Wherein, pass through the dense of the solution to metallic components
The regulation and control of degree, dosage or carrier dosage, can prepare the catalyst of specified content, this is those skilled in the art
What member was readily appreciated by.
The group VIII metallic compound is selected from one or more of the soluble compound of these metals, for example,
It can be one or more of the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
Described vib metals compound is selected from one or more of the soluble compound of these metals, for example,
It can be one or more of molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
In further preferred embodiment, organic compound object is also contained in the catalyst, example has as mentioned
Machine compound be organic carboxyl acid and its ammonium salt, described organic acid be selected from trans- 1,2-cyclohexanediaminetetraacetic acid, ethylenediamine tetra-acetic acid,
One in aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid and its ammonium salt
Kind is a variety of, and on the basis of catalyst, the content of the organic compound is 1-20 weight %.
When also containing organic compound in the catalyst, arbitrary existing method can be used and introduce them into catalysis
Agent, for example, the method using dipping introduces, such as prepares mixed solution with the mixture containing active metal, later with the solution
The method of impregnated carrier introduces, or is individually introduced with the method for the solution impregnating carrier containing the organic compound.It is described
Dipping be to prepare catalyst customary way, for example, it may be spray process impregnates, saturation dipping method and excessive liquid dipping side
Method.
After the impregnation steps are completed, can optionally be dried, roast or not roast and etc..The drying
Condition with roasting be it is conventional, for example, drying temperature be 100-300 DEG C, preferably 100-280 DEG C, drying time 1-
12 hours, preferably 2-8 hours；Maturing temperature is 350-550 DEG C, and preferably 400-500 DEG C, calcining time is 1-10 hours,
Preferably 2-8 hours.
In the present invention, to the hydrocarbon oil hydrogenation reaction condition, there is no particular limitation, and preferred reaction condition includes: anti-
Answer 200-420 DEG C of temperature, further preferably 220-400 DEG C, pressure 2-18 megapascal, further preferably 2-15 megapascal, when liquid
Air speed 0.3-10 hours-1, further preferably 0.3-5 hours-1, hydrogen to oil volume ratio 50-5000, further preferably 50-
4000。
The device of the hydrogenation reaction can be enough to urge the feedstock oil under hydrogenation conditions with described any
It is carried out in the catalytic reaction dress device of agent, for example, the reaction is in fixed bed reactors, moving-burden bed reactor or ebullated bed
It is carried out in reactor.
Catalyst activation process provided by the invention is suitable for petroleum, coal liquefaction fraction oil (for example, gasoline, boat coal, bavin
Oil etc.) hydrogenation process.
Specific embodiment
The present invention will be further illustrated in following example, but not thereby limiting the invention.
In following embodiment, analysis measurement is carried out using content of the x-ray fluorescence method to each element in catalyst
(RIPP132-90, referring to: petrochemical egineering analysis method (RIPP test methods), Yang Cui is surely equal to be compiled, Science Press, and 1990,
371-375)。
The measurement of sample crystal phase, relative crystallinity and mean grain size is referring to " solid catalyst Practical Research method " (Liu
The big volume of Wei Qiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " petrochemical egineering analysis method (RIPP test methods) " (poplar
Kingfisher is fixed, and Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405) in X-ray diffraction method carry out.
Modified boehmite and/or false boehmite used in embodiment 1-10 declaratives carrier, preparation
Method and the alumina support thus prepared.
Hydrated alumina used in experiment are as follows:
CL-A powder (false boehmite powder), opposite relative crystallinity are 100%, grain size 2.9nm, 70 weight of butt
% is measured, middle petrochemical industry Chang Ling catalyst branch is purchased from.
CL-B powder (boehmite), opposite relative crystallinity are 100%, grain size 5.2nm, 78 weight % of butt,
Purchased from middle petrochemical industry Chang Ling catalyst branch).
CL-C powder (gibbsite (α-Al2O3·3H2O)), opposite relative crystallinity is 100%, grain size 156nm, is done
65 weight % of base is purchased from middle petrochemical industry Chang Ling catalyst branch.
Wherein, 10000 grams of CL-A powder are weighed, 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 item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in sky
Under gas atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-A-Al2O3.Pass through X-ray diffraction method table
Its crystal phase, crystallinity and grain size are levied, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong,
The results are shown in Table 2.
10000 grams of CL-B powder are weighed, with 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 item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere
Under in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-B-Al2O3.Its crystalline substance is characterized by X-ray diffraction method
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, as a result arranges
In table 2.
It is obtained according to the step (1) in the method for modified boehmite of the present invention and/or false boehmite
Product of roasting are as follows:
CL-A-600: 10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-A-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
CL-A-450: 10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 3 DEG C/min of heating rate liter
CL-A-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
CL-A-400: 10000 grams of CL-A powder are weighed in a nitrogen atmosphere in Muffle furnace with 5 DEG C/min of heating rate liter
CL-A-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
CL-A-350: 10000 grams of CL-A powder are weighed and are raised in a nitrogen atmosphere with 3 DEG C/min of heating rate in baking oven
350 DEG C, and CL-A-350 is obtained within constant temperature 4 hours at 350 DEG C.
CL-B-600: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
CL-B-450: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
CL-B-400: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
CL-B-350: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-350 is obtained within constant temperature 4 hours to 350 DEG C, and at 350 DEG C.
CL-C-600: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 600 DEG C, and obtains CL-C-600 within constant temperature 4 hours at 600 DEG C.
CL-C-450: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 450 DEG C, and obtains CL-C-450 within constant temperature 6 hours at 450 DEG C.
CL-C-400: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 400 DEG C, and obtains CL-C-400 within constant temperature 6 hours at 400 DEG C.
CL-C-350: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 350 DEG C, and obtains CL-C-350 within constant temperature 6 hours at 350 DEG C.
Embodiment 1
120 grams of 350 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of A powder is 0.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 160 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S1.Pass through
X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S1.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Embodiment 2
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S2.Pass through X-ray
Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 3
Weigh respectively in terms of butt 464 grams of 109 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 4.25), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S3.Pass through X-ray
Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 4
150 grams of 100 grams of 84 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 250 grams of powder, 180 grams of CL-A-600 powder
8.10) they and 3600 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S4.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S4 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 5
200 grams of 100 grams of 140 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A- in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 450 300 grams of powder, 10 grams of CL-A-600 powder
4.36) they and 3100 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 60 DEG C of constant temperature are heated to after closed 48 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S5.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S5 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 6
100 grams of 200 grams of 70 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 400 grams of powder, 20 grams of CL-A-600 powder
10.29) they and 3200 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 100 DEG C of constant temperature are heated to after closed 24 hours；It is down to room temperature and after filtering,
Filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S6.It is characterized by X-ray diffraction method
Crystal phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S6 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 7
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220
Gram, 20 grams of CL-B-450 powder, 10 grams of CL-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 the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters,
160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains through changing
The hydrated alumina Q-S7 of property.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result arranged
In table 1.
Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S7.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Embodiment 8
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220
Gram, 20 grams of CL-B-450 powder, 10 grams of CL-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 the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters,
160 DEG C of constant temperature are heated to after closed 4 hours.It is cooled to room temperature, high pressure kettle cover is opened, 11.75 grams of ammonium dihydrogen phosphates are added,
Room temperature continues stirring 24 hours, after filtering, filter cake is 8 hours dry in 120 DEG C, obtains the modified oxygen containing auxiliary agent phosphorus
Change aluminium hydrate Q-S8.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result listed in table 1
In.
Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S8.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.It is glimmering using X
Light method measures the content of adjuvant component, and the mass fraction of the phosphate builder based on the element is 0.41%.
Embodiment 9
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues stirring 24 hours, then filters.By filter cake through 120 DEG C
It is 8 hours dry, obtain the modified hydrated alumina Q-S9 containing auxiliary agent titanium.Its crystalline substance is characterized by X-ray diffraction method
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S9 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.The content of adjuvant component, the titanium based on the element are measured using X-fluorescence method
The mass fraction of auxiliary agent is 3.12%.
Embodiment 10
320 grams of 230 grams of CL-B powder, CL-A-450 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of B powder is 1.39), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 200 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S10.It is logical
It crosses X-ray diffraction method and characterizes its crystal phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S10.Its crystal phase, relative crystallinity and crystalline substance are 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 Kong Rong, and the results are shown in Table 2.
What embodiment 11-13 illustrated that the present invention uses prepare boehmite by conventional method of modifying and/or a false water is soft
The modifier of aluminium stone and the alumina support being prepared by the modifier.
Embodiment 11
470 grams of CL-A powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 160 DEG C of constant temperature 4 is heated to after closed
Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-1.
Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
QBF-1 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S11 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 12
470 grams of CL-A-600 powder are weighed, it is mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to
In the autoclave for the stainless steel band polytetrafluoro liner that volume with stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；Drop
It is to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-2.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S12 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 13
470 grams of CL-B powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 200 DEG C of constant temperature 4 is heated to after closed
Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-3.
Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
QBF-3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S13 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and Kong Rong, the results are shown in Table 2.
Table 1
Wherein, when measuring the crystallinity of false boehmite, using CL-A powder as standard specimen；In the knot of measurement boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When measuring gama-alumina crystallinity, with CL-B-Al2O3For standard specimen.
Table 2
| Embodiment | Aluminium oxide | Specific surface area, m2/g | Kong Rong, 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 illustrates alumina support and carrier containing Y molecular sieve and its preparation of silicon oxide-containing respectively.
Embodiment 14
Then the hydrated alumina Q-S2 powder of preparation and 2 equivalent of embodiment (is purchased from middle petrochemical industry with 25 grams of silicon dioxide powders
Chang Ling catalyst branch) mixing after use banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26
(III)) being extruded into circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern item, 4 hours dry through 120 DEG C, finally horse in air atmosphere
Not be raised to 600 DEG C in furnace with 4 DEG C/min of heating rate, then 600 DEG C constant temperature 4 hours, obtain alumina support S14.
Embodiment 15
Preparation and the hydrated alumina Q-S2 powder of 2 equivalent of embodiment, then with 36 grams of Hydrogen Y molecular sieve (Na2O content
0.2%, cell parameter 2.464, relative crystallinity 88%, be purchased from middle petrochemical industry Chang Ling catalyst branch) mixing after use banded extruder
(manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into three that circumscribed circle diameter is 1.6 millimeters
Clover shape item, it is 4 hours dry through 120 DEG C, finally 600 are raised to 4 DEG C/min of heating rate in Muffle furnace in air atmosphere
DEG C, then 600 DEG C constant temperature 4 hours, obtain alumina support S15.
Embodiment 16-31 and 32-41 illustrate in the present invention using 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 (mass fraction 85%)
S1, S2 for being prepared with 199 milliliters of aqueous solution of 16.66 grams of citric acids dipping embodiment 1-15, S3, S4, S5, S6, S7,
S8, S9, S10, S11, S12, S13, S14, S15 and CL-A-Al2O3, dip time 2 hours, impregnation product was in 120 DEG C later
It is 4 hours dry, obtain catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and C16
(carrier CL-A-Al2O3)。
Embodiment 32
11 200 grams of carrier S are weighed, by the carrier S 11 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours, are catalyzed
Agent C17.
Embodiment 33
12 200 grams of carrier S are weighed, by the carrier S 12 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours, are catalyzed
Agent C18.
Embodiment 34
13 200 grams of carrier S are weighed, by the carrier S 13 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours, are catalyzed
Agent C19.
Embodiment 35
Weigh support C L-A-Al2O3200 grams, by support C L-A-Al2O3With containing 63.46 grams of ammonium metatungstates, 23.45 grams
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours of Nickelous nitrate hexahydrate, then 4 hours dry at 120 DEG C, 420 DEG C of roastings 4
Hour, obtain catalyst C20.
Embodiment 36
1 200 grams of carrier S are weighed, by the carrier S 1 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dipping above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours, obtain catalyst
C21。
Embodiment 37
11 200 grams of carrier S are weighed, by the carrier S 11 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours；Again with containing
189 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of 22.27 grams of ethylenediamine tetra-acetic acids, it is then 4 hours dry at 120 DEG C, it obtains
To catalyst C22.
Embodiment 38
12 200 grams of carrier S are weighed, by the carrier S 12 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours；Again with containing
189 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of 22.27 grams of ethylenediamine tetra-acetic acids, it is then 4 hours dry at 120 DEG C, it obtains
To catalyst C23.
Embodiment 39
13 200 grams of carrier S are weighed, by the carrier S 13 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours；Again with containing
189 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of 22.27 grams of ethylenediamine tetra-acetic acids, it is then 4 hours dry at 120 DEG C, it obtains
To catalyst C24.
Embodiment 40
Weigh support C L-A-Al2O3200 grams, by support C L-A-Al2O3With containing 63.46 grams of ammonium metatungstates, 23.45 grams
199 milliliters of aqueous solution dippings above-mentioned carrier 2 hours of Nickelous nitrate hexahydrate, then 4 hours dry at 120 DEG C, 420 DEG C of roastings 4
Hour；189 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours for containing 22.27 grams of ethylenediamine tetra-acetic acids are used again, then at 120 DEG C
It is 4 hours dry, obtain catalyst C25.
Embodiment 41
1 200 grams of carrier S are weighed, by the carrier S 1 with containing 63.46 grams of ammonium metatungstates, 23.45 grams of Nickelous nitrate hexahydrates
199 milliliters of aqueous solution dipping above-mentioned carrier 2 hours, then 4 hours dry at 120 DEG C, 420 DEG C roast 4 hours；Again with containing
189 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of 22.27 grams of ethylenediamine tetra-acetic acids, it is then 4 hours dry at 120 DEG C, it obtains
To catalyst C26.
Catalyst performance evaluation:
It evaluates comparative example 1-26 explanation and conventionally carries out catalyst vulcanization and its effect.
Catalyst is C1-C26.
Reaction carries out in 30 milliliters of fixed bed reactors, and catalyst particle size is 20~30 mesh, catalyst amount 30ml.
Catalyst vulcanization, sulfurized oil are the straight run boat coal containing 2% carbon disulfide, 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, the time 8 hours.
After vulcanization adjust reaction temperature be 360 DEG C, be passed through catalytic cracking diesel oil feedstock oil (11000 μ g/g of sulfur content,
Nitrogen content 1289 μ g/g, total 69 weight % of arene content, 39 weight % of polycyclic aromatic hydrocarbon content) it is reacted, specific reaction condition
It include: pressure 6.4MPa, reaction temperature is 360 DEG C, feed volume air speed 2h-1；Hydrogen to oil volume ratio 300.
Experiment analyzes the sulfur content in product using offline sampling, starts to sample after stable reaction 1 day (24 hours),
Then a sample was taken every 1 day, reaction continues 8 days.Obtained sample is analyzed with microcoulomb sulphur content determination instrument.As a result
It is listed in table 3.
Evaluation embodiment 1-26 illustrates the method provided by the present invention and its effect.
Catalyst is C1-C26.
Reaction carries out in 30 milliliters of fixed bed reactors, and catalyst particle size is 20~30 mesh, catalyst amount 30ml.
Activation of catalyst is carried out according to the method provided by the present invention:
Step (1): catalyst vulcanization, sulfurized oil are the straight run boat coal containing 2% carbon disulfide, and vulcanization reaction condition includes:
320 DEG C of temperature, sulfurized oil volume space velocity 2h-1Charging；Pressure 6.4MPa；Hydrogen to oil volume ratio 300, the time 8 hours.
Step (2): being purged after vulcanization, condition needed for adjusting operating condition to step (2) in purge.Its
In, blowing medium is listed in table 3.Later, inert gas is introduced, inert gas and haptoreaction condition are listed in table 3.It is used in experiment
Hydrogen and straight-run diesel oil (9800 μ g/g of sulfur content, nitrogen content 120 μ g/g, total 31 weight % of arene content, polycyclic aromatic hydrocarbon content 12
Weight %) it is blowing medium.
Hydrogenation reaction: nitrogen is switched to hydrogen, adjustment pressure is 6.4MPa；Reaction temperature is 360 DEG C；Hydrogen to oil volume ratio
300, volume space velocity 2h is pressed into reactor-1Introducing catalytic cracking diesel oil (11000 μ g/g of sulfur content, 1289 μ g/g of nitrogen content, always
Arene content 69 weight %, 39 weight % of polycyclic aromatic hydrocarbon content) reaction oil, is reacted.
Experiment analyzes the sulfur content in product using offline sampling, starts to sample after stable reaction 1 day (24 hours),
Then a sample was taken every 1 day, reaction continues 8 days.Obtained sample is analyzed with microcoulomb sulphur content determination instrument.Its
In, hydrodesulfurization activity A is calculated as follows:
A=ln [100/ (100-X)], in formula, desulfurization degree that X is.
The hydrodesulfurization activity for taking catalyst C22 conventionally to vulcanize is 100, then the opposite plus hydrogen of other catalyst
It is desulphurizing activated to can be represented by the formula:
Relative activity=(AQT/AC22) × 100%, A in formulaQTFor the activity of other catalyst, AC22For catalyst C22's
Activity.As a result it is listed in table 3.
Table 3
By table 3 the results show that the method provided by the present invention has higher hydrodesulfurization activity and stability.
Claims (10)
1. a kind of hydrogenation catalyst activation method, comprising the following steps: (1) vulcanization reaction under the conditions of, by hydrogenation catalyst with
Material reaction vulcanization containing sulfur-containing compound；(2) described by catalyst and inert gas after step (1) vulcanizes
Inert gas is selected from one or more of nitrogen, argon gas, helium, carbon dioxide and water vapour, the item with inert gas
Part includes: that pressure is normal pressure to 15 megapascal；Temperature is 200-400 DEG C, and the time is 0.5-24 hours, the volume space velocity of inert gas
For 1-1500h-1；
The hydrogenation catalyst be selected from Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst, containing carrier with
At least one to be selected from group VIII and at least one metal component selected from group VIB, the carrier is an a kind of water of modification
Softening aluminium stone and/or false boehmite formed, roast after obtained gama-alumina, the modified boehmite and/or vacation
The method of boehmite includes: that (1) roasts at least one hydrated alumina, and the roasting condition includes: that temperature is 300
DEG C -950 DEG C, the time is -24 hours 0.5 hour；(2) product of roasting for obtaining step (1) and at least one boehmite
And/or false boehmite and water mix, and obtain a kind of mixture；(3) mixture for obtaining step (2) is in confined reaction
Hydro-thermal process is carried out in device, hydrothermal conditions include: that temperature is 60 DEG C -250 DEG C, and the time is -48 hours 0.5 hour；(4) will
The product that step (3) obtains is dry, obtains modified boehmite and/or false boehmite.
2. the method according to claim 1, wherein the inert gas in nitrogen, argon gas, helium one
Kind or it is several, the condition with inert gas includes: that pressure is normal pressure to 10 megapascal；Temperature is 230-380 DEG C, and the time is
0.5-12 hours, the volume space velocity of inert gas was 10-500h-1。
3. according to the method described in claim 2, it is characterized in that, include: pressure with the condition of inert gas being normal pressure
To 6 megapascal；Time is 1-8 hours, and the volume space velocity of inert gas is 10-300h-1。
4. the method according to claim 1, wherein the vulcanization reaction condition of the step (1) includes: temperature
140-400 DEG C, -15 megapascal of pressure normal pressure, the material containing sulfur-containing compound is the gaseous mixture of hydrogen-containing gas and hydrogen sulfide,
The volume fraction of hydrogen sulfide is 0.5-15% in the gaseous mixture, and the volume space velocity of gaseous mixture is 100-3000h-1；Either, institute
State the mixture that the material containing sulfur-containing compound is sulfur-containing compound and hydrocarbon ils, the mixture of the sulfur-containing compound and hydrocarbon ils
In the mass fraction of sulfur-containing compound in terms of sulphur be 0.1-15%, the liquid hourly space velocity (LHSV) of the mixture of sulfur-containing compound and hydrocarbon ils is
0.1-20h-1。
5. according to the method described in claim 4, it is characterized in that, the vulcanization reaction condition of the step (1) includes: temperature
140-400 DEG C, -10 megapascal of pressure normal pressure, the material containing sulfur-containing compound is the gaseous mixture of hydrogen-containing gas and hydrogen sulfide,
The volume fraction of hydrogen sulfide is 3-10% in the gaseous mixture, and the volume space velocity of gaseous mixture is 300-1000h-1；Either, described
Material containing sulfur-containing compound is the mixture of sulfur-containing compound and hydrocarbon ils, in the mixture of the sulfur-containing compound and hydrocarbon ils
The mass fraction of sulfur-containing compound in terms of sulphur is 1-6%, and the liquid hourly space velocity (LHSV) of the mixture of sulfur-containing compound and hydrocarbon ils is 1-5h-1。
6. method according to claim 4 or 5, which is characterized in that the hydrocarbon ils is selected from boiling range and evaporates for 30 DEG C -350 DEG C
Divide oil.
7. the method according to claim 1, wherein the hydrogenation catalyst is Hydrobon catalyst.
8. the method according to claim 1, wherein by through step (1) vulcanization after catalyst and indifferent gas
Include the steps that displacement before body contact, replacement media is selected from hydrogen-containing gas and/or boiling range is 30 DEG C of -350 DEG C of distillates, displacement temperature
140-400 DEG C of degree, displacement pressure are normal pressure to 15 megapascal, and time swap is 1-48 hours.
9. according to the method described in claim 8, displacement pressure is normal it is characterized in that, the displacement temperature is 140-360 DEG C
10 megapascal are depressed into, time swap is 1-12 hours.
10. application of -9 any one the methods in hydrogenation reaction according to claim 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1602999A (en) * | 2004-08-24 | 2005-04-06 | 浙江大学 | Appliance exterior pre-treatment for hydrogenation catalyst |
| CN1768952A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Processing method of vessel-outside pre-sulphuring hydrogenation catalyst |
| CN1768936A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Method for preparing platinum sulfide dehydrogenation catalyst |
| CN1769377A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1602999A (en) * | 2004-08-24 | 2005-04-06 | 浙江大学 | Appliance exterior pre-treatment for hydrogenation catalyst |
| CN1768936A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Method for preparing platinum sulfide dehydrogenation catalyst |
| CN1768952A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Processing method of vessel-outside pre-sulphuring hydrogenation catalyst |
| CN1769377A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst precuring method |
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