CN106140316A - A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof - Google Patents
A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof, described hydrogenation catalyst contains the aluminium oxide shaping carrier containing adjuvant component, organic compound, at least one is selected from group VIII and at least one is selected from the metal component of vib, it is characterized in that, the described aluminium oxide shaping carrier containing adjuvant component by the boehmite containing adjuvant component of a kind of modification and/or false boehmite through molding, obtain after roasting, described boehmite containing adjuvant component and/or false boehmite are prepared by the method comprised the following steps: (1) is by least one hydrated alumina roasting；(2) product of roasting step (1) obtained and at least one boehmite and/or false boehmite, compound containing adjuvant component and water mixs, obtain one mixture；(3) mixture that step (2) obtains is carried out hydrothermal treatment consists in closed reactor；(4) product that step (3) obtains is dried.Compared with prior art, the present invention provides the catalytic performance of hydrogenation catalyst to be improved.
Description
Technical field
The present invention relates to answering of a kind of hydrogenation catalyst, the preparation method of this catalyst and this catalyst
With.
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 higher hydrodesulfurization activity with straight
The novel hydrogenation catalyst connecing desulfuration selectivity then can reduce reactive hydrogen consumption.
The activity and selectivity improving hydrogenation catalyst seeks to improve metal dispersion on the alumina support
State, and avoid the generation of low hydrogenation active metals phase species as far as possible.Alumina support is as hydrogenation
One of important component part of catalyst, its surface physico-chemical property and pore structure parameter are to hydrogenation catalyst
Catalytic performance important.And the most false boehmite of presoma preparing alumina support
And boehmite, its physical and chemical indexes has significant impact to the physico-chemical property of finished product alumina support.
It addition, the hydrogenation of catalyst also can be improved by introducing Organic substance in hydrogenation catalyst preparation process
Desulphurizing activated, such as, CN200910177170.6 provides a kind of hydrogenation catalyst and preparation method thereof,
Including step: (1) is with the solution impregnating carrier of the Thermal stability joining atom containing molybdenum and/or tungsten；(2) it is dried
The impregnation product of step (1)；(3) step is impregnated with the mixed solution of nickeliferous and/or cobalt, organic acid and ammonium ion
Suddenly the product of (2)；(4) impregnation product of drying steps (3)；Wherein, count with oxide and with catalyst as base
Standard, the aqueous solution of Thermal stability and the described step (3) of joining atom containing molybdenum and/or tungsten in described step (1)
In the nickeliferous and/or mixed solution of cobalt, organic acid and ammonium ion in the concentration of each component and the two
The consumption of solution makes the content of molybdenum and/or tungsten in final catalyst be containing of 9～30 weight %, nickel and/or cobalt
Amount is 0.5～8 weight %.The ammonium salt of described organic acid is ammonium citrate, ammonium oxalate, ammonium tartrate, ammonia
One or more in base triacetic acid ammonium, malic acid ammonium and ethylenediaminetetraacetic acid ammonium.There is provided with prior art
Catalyst compare, the catalyst hydrodesulfurization active that this invention provides is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of improved hydrogenation catalyst of performance and answers
With.
The present invention relates to herein below:
1. a hydrogenation catalyst, containing containing adjuvant component aluminium oxide shaping carrier, organic compound,
At least one is selected from group VIII and at least one is selected from the metal component of vib, it is characterised in that
The described aluminium oxide shaping carrier containing adjuvant component by the boehmite containing adjuvant component of a kind of modification and/
Or false boehmite obtains after molding, roasting, with the described boehmite containing adjuvant component and/or
On the basis of the butt of false boehmite, the mass fraction of the described adjuvant component counted with element is as 0.1%-
10%, described adjuvant component is in IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB
One or more, described boehmite containing adjuvant component and/or false boehmite are by including following step
Prepared by rapid method:
(1) by least one hydrated alumina roasting, described roasting condition includes: temperature is 300
DEG C-950 DEG C, the time is 0.5 hour-24 hours；
(2) product of roasting step (1) obtained is soft with at least one boehmite and/or a false water
Aluminum stone, compound containing adjuvant component and water mixing, obtain a kind of mixture；
(3) mixture that step (2) obtains is carried out hydrothermal treatment consists, at hydro-thermal in closed reactor
Reason condition includes: temperature is 60 DEG C-250 DEG C, and the time is 0.5 hour-48 hours；
(4) product that step (3) obtains is dried.
2. according to the catalyst described in aforementioned 1, it is characterised in that described adjuvant component selected from fluorine, phosphorus,
One or more in boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium, with described containing adjuvant component one
On the basis of the butt of boehmite and/or false boehmite, the quality of the described adjuvant component in terms of element
Mark is 0.3%-5%.
3. according to the catalyst described in aforementioned 1, it is characterised in that the roasting condition bag of described step (1)
Including: temperature is 300-750 DEG C, more preferably 350-650 DEG C, the time is 1-24 hour, further
It is preferably 2-10 hour.
4. according to the catalyst described in aforementioned 1, it is characterised in that the hydrothermal treatment consists bar of described step (3)
Part includes: temperature be 60 DEG C to less than 140 DEG C, more preferably 80-120 DEG C, the time is 0.5-48
Hour, more preferably 4-24 hour.
5. according to the catalyst described in aforementioned 1, it is characterised in that the hydrothermal treatment consists bar of described step (3)
Part includes: temperature is more than or equal to 140 DEG C extremely less than or equal to 250 DEG C, more preferably 150-
220 DEG C, the time is 0.5-48 hour, more preferably 4-24 hour.
6. according to the catalyst described in aforementioned 1, it is characterised in that the baking temperature of described step (4) is
60 DEG C-180 DEG C, more preferably 80 DEG C-150 DEG C, drying time is 0.5 hour-24 hours, enters one
Step is preferably 1 hour-12 hours.
7. according to the catalyst described in aforementioned 1, it is characterised in that described hydrated alumina is selected from a water
One or more in softening aluminium stone, false boehmite, Alumina hydrate.
8. according to the catalyst described in aforementioned 7, it is characterised in that described Alumina hydrate is three water aluminum
Stone.
9. according to the catalyst described in aforementioned 1, it is characterised in that described step (2) is by step (1)
It is mixed that the product of roasting obtained and at least one boehmite or false boehmite and water are mixed to get
In compound, solid content in mass is 1%-80%, wherein, and described product of roasting and in terms of butt
The mass ratio of boehmite or false boehmite is 0.1-20.
10. according to the catalyst described in aforementioned 9, it is characterised in that described step (2) is by step (1)
It is mixed that the product of roasting obtained and at least one boehmite or false boehmite and water are mixed to get
In compound, solid content in mass is 5%-70%, wherein, described product of roasting with in terms of butt
The mass ratio of boehmite or false boehmite is 0.2-12.
11. according to the catalyst described in aforementioned 1, it is characterised in that described group VIII metal component is selected from
Nickel and/or cobalt, the metal component of vib is selected from molybdenum and/or tungsten, on the basis of catalyst, described VIII
The content of race's metal component is 1-10 weight %, and the content of vib metals component is 5-40 weight %.
12. according to the catalyst described in aforementioned 11, it is characterised in that on the basis of catalyst, and described
The content of group VIII metal component is 1.5-6 weight %, and the content of vib metals component is 10-35 weight
%.
13. according to the catalyst described in aforementioned 1, it is characterised in that described organic compound is selected from organic carboxylic
Acid, organic carboxyl acid ammonium salt in one or more, on the basis of catalyst, described organic compound
Content is 0.1-30 weight %.
14. according to the catalyst described in aforementioned 13, it is characterised in that described organic carboxyl acid is selected from trans 1,
2-1,2-diaminocyclohexane tetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, first
One or more in acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid, with catalyst as base
Standard, the content of described organic compound is 1-20 weight %.
15. catalyst according to claim 1, it is characterised in that in described aluminium oxide shaping carrier
Containing clay and/or molecular sieve, on the basis of described carrier, described clay and/or the mass fraction of molecular sieve
It is less than 35%.
16. catalyst according to claim 15, it is characterised in that on the basis of described carrier,
The mass fraction of described clay and/or molecular sieve is 1%-20%.
17. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, are contacted instead with catalyst by hydrocarbon ils
Should, it is characterised in that described catalyst is the catalyst described in aforementioned any one.
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, exists for one
There is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse in 14.5 ° ± 0.5 ° (2 θ).
Described boehmite is also called boehmite, characterizes with X-ray diffraction, exists for one
There is the alumina hydration of the strongest, narrow and sharp-pointed (020) crystallographic plane diffraction peak in 14.5 ° ± 0.5 ° (2 θ)
Thing (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, compound containing adjuvant component and water mixing, obtain a kind of mixture, and should
Mixture in 60 DEG C of-250 DEG C of hydrothermal treatment consists 0.5-48 hour, is preferable over 80-220 DEG C of water in hermetic container
Heat treatment 4-24 hour, the thus modified boehmite obtained and/or the relative crystallization of false boehmite
Degree improves, and the most fired aluminium oxide obtained maintains higher specific surface area and pore volume.
In a specific embodiment, the product of roasting that step (1) is obtained by described step (2) with at least
In the mixture that a kind of boehmite or false boehmite and water are mixed to get, the most in mass
Solid content be 1%-80%, wherein, described product of roasting and the boehmite in terms of butt or false one
The mass ratio of boehmite is 0.1-20.Step (1) is obtained by further preferred described step (2)
The mixture that product of roasting and at least one boehmite or false boehmite and water are mixed to get
In, solid content in mass is 5%-70%, wherein, and described product of roasting and the water in terms of butt
The mass ratio of softening aluminium stone or false boehmite 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.
Wherein, when controlling hydrothermal treatment consists temperature and being more than 140 DEG C, gained modified product is the soft aluminum of water
Stone；When controlling hydrothermal treatment consists temperature less than 140 DEG C, the crystalline phase of products therefrom keeps one with initiation material
Cause.
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
For 150-220 DEG C, 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, excellent
Select 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), under conditions of 2-10 hour, the present invention is to the method for roasting described in step (1) the most especially
Limit.For example, it may be by described hydrated alumina in usual baking oven or roaster at air gas
Carry out roasting under atmosphere, it is also possible to be in the baking oven or roaster of vacuum-pumping under vacuum or be passed through
Carry out under inert gas conditions.When described roasting is passed through noble gas, described noble gas can be to appoint
The not oxygen-containing gas that be enough to gasify under described roasting condition of meaning, such as, can be selected from nitrogen, argon
One or more in gas, 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.
In the present invention, described adjuvant component selected from IIIA, IVA, VA, VIIA, IIA, IIB,
One or more in IIIB, Group IVB, fluorine preferably wherein, phosphorus, boron, silicon, magnesium, zinc, lanthanum,
One or more in cerium, titanium and zirconium.Described in terms of butt boehmite containing adjuvant component and/
Or on the basis of false boehmite, the mass fraction of the described adjuvant component counted with element as 0.1%-10%,
It is preferably 0.3-5%, more preferably 0.3-4%.
The described compound containing adjuvant component, preferably their water soluble compound, the example of this compound
Son is such as: Fluohydric acid., ammonium fluoride, Fluohydric acid. ammonium, hexafluosilicic acid, ammonium fluosilicate, boric acid, ammonium borate, partially
Ammonium borate, tetraboric acid ammonium, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, boric acid, tetraboric acid
Ammonium, Ludox, Silicon chloride., ammonium fluosilicate and tetraethyl orthosilicate, magnesium nitrate, magnesium acetate, sulphuric acid
Magnesium, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, chlorination
Zinc, Lanthanum (III) nitrate, lanthanum carbonate, lanthanum chloride, cerous nitrate, cerous carbonate, cerium chloride, titanium sulfate, four chlorinations
Titanium, titanous chloride., butyl titanate, zirconium nitrate, zirconyl nitrate and zirconium oxychloride etc..
Compared with prior art, the modified boehmite and/or false that method provided by the present invention obtains
Boehmite is improving relative crystallinity simultaneously, can effectively suppress the growth of crystal grain, to a certain extent
Realize the regulation and control to modified product grain growth.This modification boehmite and/or false boehmite are through roasting
Available high-specific surface area and the alumina support of pore volume after burning.
One or more in organic carboxyl acid and ammonium salt thereof of described organic compound, with catalyst as base
Standard, the content of described organic compound is 0.1-30 weight %.The most described organic carboxyl acid is selected from trans 1,
2-1,2-diaminocyclohexane tetraacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, first
One or more in acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid, with catalyst as base
Standard, the content of described organic compound is 1-20 weight %.
In the present invention, described hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or
Hydrocracking catalyst.In described catalyst selected from group VIII with selected from the metal component of vib
Selecting for routine, such as, described group VIII metal component is selected from cobalt and/or nickel, vib metals component
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 %.
In the present invention, by described organic compound, at least one group VIII and at least one vib
It is method customary in the art that metal component is carried on the method on carrier, for example, it may be will organise
Compound, be configured to solution containing group VIII and/or vib metals compound after impregnate the side of described carrier
Method；Can be by organic compound, individually prepare molten containing group VIII or vib metals compound
The method impregnating carrier after liquid.Wherein, by concentration, consumption or the carrier of the solution to metallic components
The regulation of consumption and control, can prepare the described catalyst specifying content, and this is people in the art
Member is readily appreciated by.
According to the present invention, after described impregnation steps completes, optionally can be dried, roasting or
The steps such as not roasting.The described condition being dried with roasting is all conventional, and such as, baking temperature is 100-
300 DEG C, preferably 100-280 DEG C, drying time is 1-12 hour, preferably 2-8 hour；Roasting temperature
Degree is for 350-550 DEG C, and preferably 400-500 DEG C, roasting time is 1-10 hour, and preferably 2-8 is little
Time.
Described dipping is for preparing catalyst customary way, for example, it may be spray process dipping, saturated
Dipping method and excess liquid dipping method.
In the present invention, described aluminium oxide shaping carrier can contain clay and/or molecular sieve, with described load
On the basis of body, the mass fraction of described clay and/or molecular sieve is less than 35%, preferably 1%-20%.
When in described aluminium oxide shaping carrier containing clay and/or molecular sieve, carry in described aluminium oxide molding
The preparation process of body includes introducing clay and/or the step of molecular sieve, described introducing clay and/or molecular sieve
Method thing conventional method.Such as, described clay and/or molecular sieve are selected from three aqua oxidations with described
The mixture of one or more in aluminum, monohydrate alumina and amorphous hydroted alumina is through molding roasting
Rear prepared.
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.
In described catalyst, the content of carrier is to well known to a person skilled in the art.Total amount with catalyst
On the basis of, in terms of oxide, in described catalyst, the content of carrier can be 60-90.5 weight %.
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.
The catalyst provided according to the present invention, the most in presence of hydrogen, in 140-370 DEG C
At a temperature of carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also outside device
Can be In-situ sulphiding in device, the active metal component it loaded is converted into metal sulfide component.
In the present invention, to described hydrotreating 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 using the present invention to provide can process all kinds of hydrocarbon oil crude material.Such as, described hydrocarbon oil crude material
Can be various heavy mineral oil or artificial oil or their mixed fraction oil, such as selected from crude oil, fraction
Oil (gasoline, kerosene, diesel oil etc.), solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, coal
One or more in liquefaction oil, frivolous coal tar and heavy deasphalted oil.
In the present invention, described direct desulfurization refers to thiophene sulfocompounds, it is not necessary to the most saturated containing thia
All of carbon-carbon double bond on ring, and directly the sulphur atom on sulfur heterocyclic ring is realized desulfurization by hydrogenolysis.Example
As, it is considered that, the hydrodesulfurization reaction of dibenzothiophenes is carried out according to two kinds of reaction paths: path
I is that directly the sulphur atom in removing dibenzothiophenes molecule generates biphenyl, referred to as direct desulfurization (or hydrogenolysis
Desulfurization)；Path II is first the benzene ring hydrogenation of dibenzothiophenes to be generated hexahydro dibenzothiophenes, then takes off
Except the sulphur atom in hexahydro dibenzothiophenes molecule generates cyclohexyl benzene, the most pre-hydrodesulfurization.Raising adds
The direct desulfurization selectivity of hydrogen catalyst will assist in and reduces carbon carbon unnecessary in oil hydrogenation sweetening process
Double-bond hydrogenation is saturated, thus reduces hydrogen consumption.
Compared with existing catalyst, the aluminium oxide that the present invention provides is that catalyst prepared by carrier has preferably
Hydrodesulfurization activity and higher direct desulfurization selectivity.
Such as, the mixed solution with the n-decane containing dibenzothiophenes (DBT) 0.58 weight % is former
Material, the catalyst and the comparative catalyst that provide the present invention carry out hydrodesulfurization activity comparative evaluation, with right
Be 100 than hydrodesulfurization activity and the direct desulfurization selectivity of catalyst, then the present invention provides catalyst
Relative hydrodesulfurization activity be 115, relatively direct desulfuration selectivity is up to 114.Obviously, along with desulfurization
React and increase with the selectivity of direct desulfurization, it will help it is unnecessary to reduce in oil hydrogenation sweetening process
Carbon-carbon double bond hydrogenation is saturated, and produced direct result is exactly that the hydrogen consumption making desulphurization reaction reduces.
Detailed description of the invention
Example below will be further illustrated the present invention, but not thereby limiting the invention.
In the present invention, the mensuration of sample crystalline phase, degree of crystallinity and mean grain size is with reference to " solid catalyst is real
With research method " (the big volume of Liu Weiqiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " stone
Oiling work point analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying, Wu Wenhui compile, and science goes out
Version society, 1990,394-405) in X-ray diffraction method.
X-fluorescence method is used to measure the content of adjuvant component.
The hydrated alumina used in experiment is:
CL-A powder (false boehmite powder), 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 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 crystallinity is 100%, and crystal grain is big
Little 156nm, butt 65 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.
Weigh 10000 grams of CL-A powder, 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 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-A-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.
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.
The product of roasting obtained according to the step (1) in offer method of the present invention 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.
Modified boehmite that embodiment 1-10 declaratives carrier is used and/or false boehmite,
Its preparation method and the alumina support thus prepared.
Embodiment 1
Weigh 364 grams of CL-A powder in terms of butt, 110 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 0.30 with the mass ratio of the powder of CL-A in terms of butt), they are mixed with 3600 grams of deionized waters,
And add 10.78 grams of ammonium dihydrogen phosphates, stir into serosity；The volume that this serosity is transferred to band stirring is 5
In the autoclave of the stainless steel band polytetrafluoro liner risen, airtight post-heating to 160 DEG C constant temperature 4 hours；Fall
To room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the aqua oxidation containing auxiliary agent
Aluminum Q-S1.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, result is listed in table
In 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, degree of crystallinity and grain size, and the results are shown in Table 1.Pass through N2
Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 2
Weigh 235 grams of CL-A powder in terms of butt, 296 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 1.26 with the mass ratio of the CL-A powder in terms of butt), they are mixed with 3600 grams of deionized waters
Close, and add 12.08 grams of ammonium dihydrogen phosphates, stir into serosity；This serosity is transferred to the appearance of band stirring
Amass is that in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, airtight post-heating to 160 DEG C constant temperature 4 is little
Time；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the water containing auxiliary agent
Close aluminium oxide Q-S2.Its crystalline phase, degree of crystallinity and grain size, result is characterized by X-ray diffraction method
It is 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, 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.
Embodiment 3
Weigh 126 grams of CL-A powder in terms of butt, 453 grams of (CL-A-600 powder of CL-A-600 powder respectively
It is 3.60 with the mass ratio of the CL-A powder in terms of butt), and add 13.21 grams of ammonium dihydrogen phosphates, will
They are mixed into serosity with 3600 grams of deionized waters；The volume that this serosity is transferred to band stirring is 5
In the autoclave of the stainless steel band polytetrafluoro liner risen, airtight post-heating to 160 DEG C constant temperature 4 hours；Fall
To room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the aqua oxidation containing auxiliary agent
Aluminum Q-S3.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, result is listed in table
In 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, 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.
Embodiment 4
Weigh 88 grams of CL-A powder in terms of butt, 110 grams of CL-A-350 powder, CL-A-400 powder respectively
147 grams, 248 grams of CL-A-450 powder, 178 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 7.81), they are mixed with 3600 grams of deionized waters,
And add 51.12 grams of titanium sulfates, stir into serosity；The volume that this serosity is transferred to band stirring is 5 liters
In the autoclave of stainless steel band polytetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room
Temperature after filtering, filter cake is dry 8 hours in 120 DEG C, obtain the hydrated alumina Q-containing auxiliary agent
S4.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, result is listed in table 1
In.
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, 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.
Embodiment 5
Weigh 146 grams of CL-A powder in terms of butt, 102 grams of CL-A-350 powder, CL-A-400 powder respectively
185 grams, 295 grams of CL-A-450 powder, 8 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with
The mass ratio of the CL-A powder of butt meter is 4.05), they are mixed with 3100 grams of deionized waters, and
Add 20.56 grams of zinc nitrate hexahydrates, 49.12 grams of magnesium nitrate hexahydrates and 10.56 grams of ammonium fluorides, stirring
Become serosity；This serosity is transferred to the high pressure of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring
In 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 containing auxiliary agent.By X-ray diffraction method
Characterizing its crystalline phase, degree of 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, 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.
Embodiment 6
Weigh 77 grams of CL-A powder in terms of butt, 205 grams of CL-A-350 powder, CL-A-400 powder respectively
96 grams, 396 grams of CL-A-450 powder, 18 grams of CL-A-600 powder (total amount of CL-A-350～600 powder with
The mass ratio of the CL-A powder of butt meter is 9.29), they are mixed with 3200 grams of deionized waters, and
Add 14.67 grams of lanthanum nitrate hexahydrates and 15.32 gram of six nitric hydrate cerium, stir into serosity；By this serosity
In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters transferring to band stirring, airtight post-heating
To 100 DEG C of constant temperature 24 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C,
Obtain the hydrated alumina Q-S6 containing auxiliary agent.Its crystalline phase, degree of crystallinity is characterized by X-ray diffraction method
And grain size, 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, 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.
Embodiment 7
Weigh 64 grams of CL-A powder in terms of butt, 20 grams of CL-B powder, CL-A-350 powder 62 respectively
Gram, 18 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400
35 grams of powder, 15 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 8.10 with the mass ratio of the CL powder in terms of butt), by they with
3600 grams of deionized water mixing, and add 29.76 grams of boric acid, stir into serosity；This serosity is transferred to
In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters of band stirring, airtight post-heating is extremely
160 DEG C of constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains
Hydrated alumina Q-S7 containing auxiliary agent.Its crystalline phase, degree of crystallinity and crystalline substance is characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.
Q-S7 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 S7.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.
Embodiment 8
Weigh 64 grams of CL-A powder in terms of butt, 20 grams of CL-B powder, CL-A-350 powder 62 respectively
Gram, 18 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400
35 grams of powder, 15 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 8.10 with the mass ratio of the CL powder in terms of butt), by they with
3600 grams of deionized water mixing, add 85.58 grams of Ludox and (containing silicon dioxide 30 weight %, are purchased from
Haiyang Chemical Plant, Qingdao), stir 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, after filtration, filter cake is dried 8 hours in 120 DEG C, obtains containing auxiliary agent
Hydrated alumina powder Q-S8.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.
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, degree of crystallinity and grain size, and the results are shown in Table 1.Pass through N2
Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 9
Weigh 64 grams of CL-A powder in terms of butt, 20 grams of CL-B powder, CL-A-350 powder 62 respectively
Gram, 18 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, CL-B-400
35 grams of powder, 15 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 8.10 with the mass ratio of the CL powder in terms of butt), by they with
3600 grams of deionized water mixing, add 83.98 gram of eight hydration zirconium oxychloride, stir into serosity；Should
Serosity transfer to band stirring the stainless steel band polytetrafluoro liner that volume is 5 liters autoclave in, airtight after
It is heated to 160 DEG C of constant temperature 4 hours.After being down to room temperature, high pressure kettle cover is opened, after filtration, by filter cake
It is dried 8 hours in 120 DEG C, obtains the hydrated alumina powder Q-S9 containing auxiliary agent.Spread out by X-ray
Shooting method characterizes its crystalline phase, degree of crystallinity and grain size, and the results are shown in Table 1.
By Q-S9 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 S9 in air atmosphere.Pass through
X-ray diffraction method characterizes its crystalline phase, degree of crystallinity and grain size, and the results are shown in Table 1.Pass through N2
Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 10
Weigh 230 grams of CL-B powder in terms of butt, 300 grams of (CL-A-600 powder of CL-A-450 powder respectively
It is 1.30 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, and add 9.08 grams of ammonium dihydrogen phosphates, stir into serosity；This serosity is transferred to band stirring
The stainless steel band polytetrafluoro liner that volume is 5 liters autoclave in, airtight post-heating to 200 DEG C, and
Under agitation constant temperature 4 hours；Afterwards, it is down to room temperature after filtering, filter cake is dried 8 in 120 DEG C little
Time, obtain the product Q-S10 being modified.Characterize its crystalline phase by X-ray diffraction method, relatively crystallize
Degree and grain size, the results are shown in Table 1.
By 0-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.
The explanation of comparative example 1-3 is prepared changing of boehmite and/or false boehmite by conventional method of modifying
Property thing and the alumina support prepared by this modifier.
Comparative example 1
Weigh 474 grams of CL-A powder in terms of butt, it is mixed with 3600 grams of deionized waters, and adds
10.89 grams of ammonium dihydrogen phosphates, stir 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 QBF-being modified
1.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, result is listed in table 1
In.
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 DS1.Its crystalline phase, degree of crystallinity and crystal grain is characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and result is listed in
In table 2.
Comparative example 2
Weigh 474 grams of CL-A-600 powder, it is mixed with 3600 grams of deionized waters, and adds 10.89 grams
Ammonium dihydrogen phosphate, stirs into serosity；This serosity is transferred to the stainless steel band that volume is 5 liters of band stirring
In the autoclave of polytetrafluoro liner, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature and passes through
After filter, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina QBF-2 being modified.Pass through
X-ray diffraction method characterizes its crystalline phase, degree of crystallinity and grain size, and 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 DS2.Its crystalline phase, degree of crystallinity and crystal grain is characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and result is listed in
In table 2.
Comparative example 3
Weigh 530 grams of CL-B powder in terms of butt, it is mixed with 3600 grams of deionized waters, and adds
9.08 grams of ammonium dihydrogen phosphates, stir 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 200 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 QBF-being modified
3.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, result is listed in table 1
In.
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 DS3.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.
The degree of crystallinity of table 1 aluminium oxide and grain size
Wherein, when measuring the degree of crystallinity of false boehmite, with CL-A powder as standard specimen；Measuring one
During the degree of crystallinity of boehmite, with CL-B powder as standard specimen；When measuring gama-alumina degree of crystallinity, with CL-
B-Al2O3For standard specimen.
The specific surface area of table 2 aluminium oxide and pore volume
| 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 | 264 | 0.67 |
| 2 | S2 | 249 | 0.63 |
| 3 | S3 | 225 | 0.62 |
| 4 | S4 | 246 | 0.63 |
| 5 | S5 | 276 | 0.69 |
| 6 | S6 | 268 | 0.67 |
| 7 | S7 | 227 | 0.62 |
| 8 | S8 | 232 | 0.62 |
| 9 | S9 | 255 | 0.64 |
| 10 | S10 | 195 | 0.61 |
| Comparative example 1 | DS1 | 234 | 0.53 |
| Comparative example 2 | DS2 | 175 | 0.60 |
| Comparative example 3 | DS3 | 133 | 0.46 |
The catalyst of embodiment 11-23 explanation present invention offer and preparation thereof.
Embodiment 11-20
Respectively with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49 grams of phosphoric acid (divide by quality
Several 85%) it is prepared into 16.20 grams of Fructus Citri Limoniae aqueous acids, 200 grams of embodiments 1-10 of 199 milliliters of dippings
S1, S2, S3, S4, S5, S6, S7, S8, S9 and the S10 arrived, dip time 2 hours, afterwards
Impregnation product in 120 DEG C be dried 4 hours, obtain catalyst C1, C2, C3, C4, C5, C6,
C7, C8, C9 and C10.
Embodiment 21
With containing 28.22 grams of MoO3, 1.28 grams of trans CDTA, 3.56 grams of ethylenediamines
Ammonia spirit 199 milli of tetraacethyl, 2.58 grams of malic acids, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates
Rising the S1 that dipping embodiment 1 prepares, impregnation product is dried 4 hours in 120 DEG C afterwards；The most again
Molten with the ammonia containing 22.86 grams of cabaltous nitrate hexahydrates, 17.82 grams of ethylenediaminetetraacetic acid and 3.26 grams of ammonium oxalate
Liquid 199 milliliters impregnates above-mentioned carrier, dip time 2 hours, and impregnation product is dried 4 little in 120 DEG C afterwards
Time, obtain catalyst C11.
Embodiment 22
With containing 28.22 grams of MoO3,0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acid, 1.56 grams of formic acid and
The S1 that the ammonia spirit of 36.23 grams of citric acids 199 milliliters dipping embodiment 1 prepares, impregnates product afterwards
Thing is dried 4 hours in 120 DEG C；The most again with containing 22.86 grams of cabaltous nitrate hexahydrates, 21.27 grams of ethylenediamines
The ammonia spirit of tetraacethyl and 1.86 grams of aminotriacetic acids 199 milliliters impregnates above-mentioned carrier, dip time 2
Hour, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C12.
Embodiment 23
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 S11.
Weigh carrier S 11200 grams, with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49
Gram phosphoric acid (mass fraction 85%) and 199 milliliters of dippings of 16.20 grams of Fructus Citri Limoniae aqueous acids, during dipping
Between 2 hours, afterwards impregnation product in 120 DEG C be dried 4 hours, obtain catalyst C13.
Comparative example 4-7 explanation reference catalyst and preparation thereof.
Respectively with containing 28.22 grams of MoO3, 22.86 grams of cabaltous nitrate hexahydrates, 2.49 grams of phosphoric acid (divide by quality
Several 85%) and 16.20 grams of Fructus Citri Limoniae aqueous acids 199 milliliters, 200 grams of carrier DS1 of dipping, DS2,
DS3 and CL-A-Al2O3, dip time 2 hours, impregnation product is dried 4 hours in 120 DEG C afterwards,
Obtain catalyst D1, D2, D3 and D4.
Catalyst performance evaluation:
The hydrogenation evaluating the reference catalyst that embodiment 11-23 provides catalyst and comparative example 4-7 to provide takes off
Sulfur performance, result is listed in table 3.
With the mixed solution of the n-decane containing dibenzothiophenes (DBT) 0.58 weight % as raw material, at height
The upper evaluation of pressure micro-reactor (manufacturer: Beijing petrochemical industry information automation company, model: DADI) is urged
The hydrodesulfurization activity of agent, becomes the granule of a diameter of 40-60 mesh, the dress of catalyst by catalyst breakage
The amount of filling out is 0.15 gram.
Before formal charging, first with the hexamethylene containing 5 weight % Carbon bisulfide for sulfurized oil respectively to catalysis
Agent carries out presulfurization, and the condition of presulfurization includes: pressure is 4.14MPa, and temperature is 362 DEG C, and the time is
3.5 hours, sulfurized oil feed rate was 0.2 ml/min.
After sulfuration terminates, being cooled to reaction temperature is 282 DEG C, cuts raw material.Reaction condition includes: former
Material feed rate is 0.2 ml/min, and hydrogen dividing potential drop is 4.14Mpa, and hydrogen to oil volume ratio is 900.Reaction 3
Sample in high-pressure separator exit after hour.Gained sample Agilent6890N-MASS gas chromatogram-
Mass spectrograph is analyzed, and the results are shown in Table 1.Wherein, the hydrodesulfurization activity A of DBT is calculated as follows:
A=ln [100/ (100-X)],
In formula, X is the conversion ratio of DBT
The hydrodesulfurization activity of the DBT taking comparative catalyst D4 is 100, then other catalyst is relative
The hydrodesulfurization activity of DBT can be represented by the formula:
Relative activity=(AQT/AD4) × 100%,
A in formulaQTFor the activity of other catalyst, AD4Activity for reference catalyst.
Direct desulfurization selectivity S is as the ratio of both biphenyl in hydrodesulfurization reaction product and cyclohexyl benzene content
Value calculates.
The direct desulfurization selectivity of the DBT taking comparative catalyst D4 is 100, then the phase of other catalyst
The direct desulfurization selectivity of DBT be can be represented by the formula:
Relatively direct desulfuration selectivity=(SQT/SD4) × 100%.
Table 3
Shown by the result of table 3, all show preferably hydrogenation according to the hydrogenation catalyst of the present invention de-
Active and the higher direct desulfurization selectivity of sulfur.
Claims (17)
1. a hydrogenation catalyst, containing containing adjuvant component aluminium oxide shaping carrier, organic compound,
At least one is selected from group VIII and at least one is selected from the metal component of vib, it is characterised in that
The described aluminium oxide shaping carrier containing adjuvant component by the boehmite containing adjuvant component of a kind of modification and/
Or vacation boehmite obtains through molding, roasting, with the described boehmite containing adjuvant component and/or vacation
On the basis of the butt of boehmite, the mass fraction of the described adjuvant component counted with element is as 0.1%-
10%, described adjuvant component is in IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB
One or more, described boehmite containing adjuvant component and/or false boehmite are by including following step
Prepared by rapid method:
(1) by least one hydrated alumina roasting, described roasting condition includes: temperature is 300
DEG C-950 DEG C, the time is 0.5 hour-24 hours；
(2) product of roasting step (1) obtained is soft with at least one boehmite and/or a false water
Aluminum stone, compound containing adjuvant component and water mixing, obtain a kind of mixture；
(3) mixture that step (2) obtains is carried out hydrothermal treatment consists, at hydro-thermal in closed reactor
Reason condition includes: temperature is 60 DEG C-250 DEG C, and the time is 0.5 hour-48 hours；
(4) product that step (3) obtains is dried.
Catalyst the most according to claim 1, it is characterised in that described adjuvant component selected from fluorine,
One or more in phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium, with described containing adjuvant component
Boehmite and/or false boehmite butt on the basis of, the described adjuvant component in terms of element
Mass fraction is 0.3%-5%.
Catalyst the most according to claim 1, it is characterised in that the roasting bar of described step (1)
Part includes: temperature is 300-750 DEG C, more preferably 350-650 DEG C, and the time is 1-24 hour, enters
One step is preferably 2-10 hour.
Catalyst the most according to claim 1, it is characterised in that at the hydro-thermal of described step (3)
Reason condition includes: temperature be 60 DEG C to less than 140 DEG C, more preferably 80-120 DEG C, the time is
0.5-48 hour, more preferably 4-24 hour.
Catalyst the most according to claim 1, it is characterised in that at the hydro-thermal of described step (3)
Reason condition includes: temperature is more than or equal to 140 DEG C extremely less than or equal to 250 DEG C, more preferably 150-
220 DEG C, the time is 0.5-48 hour, more preferably 4-24 hour.
Catalyst the most according to claim 1, it is characterised in that the baking temperature of described step (4)
Being 60 DEG C-180 DEG C, more preferably 80 DEG C-150 DEG C, drying time is 0.5 hour-24 hours, enters
One step is preferably 1 hour-12 hours.
Catalyst the most according to claim 1, it is characterised in that described hydrated alumina is selected from
One or more in boehmite, false boehmite, Alumina hydrate.
Catalyst the most according to claim 7, it is characterised in that described Alumina hydrate is three
Diaspore.
Catalyst the most according to claim 1, it is characterised in that described step (2) is by step
(1) product of roasting obtained and at least one boehmite or false boehmite and water are mixed to get
Mixture in, solid content in mass is 1%-80%, wherein, described product of roasting with in terms of butt
Boehmite or the mass ratio of false boehmite be 0.1-20.
Catalyst the most according to claim 9, it is characterised in that described step (2) is by step
(1) product of roasting obtained and at least one boehmite or false boehmite and water are mixed to get
Mixture in, solid content in mass is 5%-70%, wherein, described product of roasting with butt
The boehmite of meter or the mass ratio of false boehmite are 0.2-12.
11. catalyst according to claim 1, it is characterised in that described group VIII metal component
Selected from nickel and/or cobalt, the metal component of vib is selected from molybdenum and/or tungsten, on the basis of catalyst, described
The content of group VIII metal component is 1-10 weight %, and the content of vib metals component is 5-40 weight
%.
12. catalyst according to claim 11, it is characterised in that on the basis of catalyst, institute
The content stating group VIII metal component is 1.5-6 weight %, and the content of vib metals component is 10-35
Weight %.
13. catalyst according to claim 1, it is characterised in that described organic compound is selected from having
Machine carboxylic acid, organic carboxyl acid ammonium salt in one or more, on the basis of catalyst, described organic compound
The content of thing is 0.1-30 weight %.
14. catalyst according to claim 13, it is characterised in that described organic carboxyl acid is selected from anti-
Formula CDTA, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, second
One or more in acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid, with catalyst
On the basis of, the content of described organic compound is 1-20 weight %.
15. catalyst according to claim 1, it is characterised in that in described aluminium oxide shaping carrier
Containing clay and/or molecular sieve, on the basis of described carrier, described clay and/or the mass fraction of molecular sieve
It is less than 35%.
16. catalyst according to claim 15, it is characterised in that on the basis of described carrier,
The mass fraction of described clay and/or molecular sieve is 1%-20%.
17. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, are contacted instead with catalyst by hydrocarbon ils
Should, it is characterised in that described catalyst is the catalyst described in claim 1-16 any one.
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| CN201510178123.9A CN106140316B (en) | 2015-04-15 | 2015-04-15 | A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation |
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| CN201510178123.9A CN106140316B (en) | 2015-04-15 | 2015-04-15 | A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106635139A (en) * | 2017-01-13 | 2017-05-10 | 武汉科林精细化工有限公司 | Application of catalyst in hydrogenation of crude benzene and coal-based naphtha mixture |
| CN110372004A (en) * | 2019-07-29 | 2019-10-25 | 中国石油大学(北京) | A kind of the regulation method and application of the microcosmic aluminium distribution of ZSM-5 molecular sieve |
| JP2020527104A (en) * | 2017-07-21 | 2020-09-03 | アルベマール ヨーロッパ エスアールエル | Hydrogenation catalyst containing titanium-containing carriers and organic additives |
| CN112742404A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method |
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| CN106635139A (en) * | 2017-01-13 | 2017-05-10 | 武汉科林精细化工有限公司 | Application of catalyst in hydrogenation of crude benzene and coal-based naphtha mixture |
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| CN112742404B (en) * | 2019-10-31 | 2023-07-14 | 中国石油化工股份有限公司 | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method |
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| CN106140316B (en) | 2018-09-28 |
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