CN105268449B - A kind of hydrogenation catalyst and its application in hydrogenation deoxidation - Google Patents
A kind of hydrogenation catalyst and its application in hydrogenation deoxidation Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and its application in hydrogenation deoxidation, the catalyst contains the molybdenum and/or tungsten metal component and nickel and/or cobalt metal component selected from group VIII selected from vib of the alumina support and load of one or more of promoter metal components in IA, IIA, Group IVB on this carrier, on the basis of the total amount of the carrier, the mass fraction of the promoter metal component counted using element is 0.5% 5%.The shaping of modification hydrated alumina, dry, roasting the method preparation containing the alumina support containing one or more of promoter metal components in IA, IIA, Group IVB by a kind of one or more of promoter metal components containing in IA, IIA, Group IVB.Compared with existing catalyst, the catalyst that the present invention is provided has higher hydrogenation deoxidation activity and stability.
Description
Technical field
A kind of application the present invention relates to hydrogenation catalyst and its in hydrogenation deoxidation.
Background technology
Coal directly converts the oxygen content such as oil, Fischer-Tropsch synthesis oil, oil shale and bio oil height, and high oxygen content directly affects oil
The quality of product is, it is necessary to carry out hydrogenation deoxidation reaction, to remove oxygenatedchemicals therein.
CN 201210237740.8 discloses a kind of non-loading type nano hydrogenation dehydrogenation catalyst, what the catalyst was used
Be nickel, molybdenum, tungsten compound be active component presoma, required presoma through mechanical ball mill, calcining after with metal sulfide
Form constitute catalyst, required presoma each component constitutes by mass percentage：Nickel nitrate 3%-40%, molybdenum oxide 1%-
40%, tungsten oxide 1%-70%, sulphur 5%-70%.Using the method for cycle annealing after high-energy ball milling under being acted in protective atmosphere,
Nanocatalyst body granules are made.It is said that the catalyst has high activity, high deoxidation selectivity, high stability and producer
Method is simple, with low cost, can be widely applied to the hydrogenation deoxidation essence of the various new substitute energy source for petroleum such as coal liquifaction, bio oil
System.
CN 201210153043.4 discloses a kind of high dispersive bifunctional catalyst and its system for phenol hydrogenation deoxidation
Preparation Method.The catalyst is to be loaded active metal Pt by in-situ synthetic method by complexing agent mercaptopropyl trimethoxysilane
Formed on the ordered mesoporous molecular sieve Al-SBA-15 (x) being modified through Al, be expressed as 1%Pt- (SH)/Al-SBA-15 (x)；Its
In 1% represent Pt mass fractions in the catalyst；X represents the silica alumina ratio in Al-SBA-15, and its span is 7-
300.It is said that using the catalyst phenol hydrogenation deoxidation reaction in optimal conditions conversion ratio up to 100.0%, the choosing of hexamethylene
Selecting property is up to 99.0%.
In view of the Cost Problems of catalyst, what is mainly used during industrial progress hydrogenation deoxidation reaction at present is still load
The non-noble metal sulfided state catalyst of type, for example, NiMo/ γ-Al2O3Or CoMo/ γ-Al2O3Deng.This kind of catalyst typically has
Higher hydrodesulfurization and hydrodenitrogenationactivity activity, while they also have higher initial activity to hydrogenation deoxidation.But, it is this kind of to urge
Agent is applied to less stable during hydrogenation deoxidation, it is easy to inactivate.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of new hydrogenation catalyst and its application in hydrogenation deoxidation.
Content of the present invention includes：
1. a kind of hydrogenation catalyst, containing containing one or more of promoter metal components in IA, IIA, Group IVB
The molybdenum and/or tungsten metal component and the nickel selected from group VIII selected from vib of alumina support and load on this carrier
And/or cobalt metal component, on the basis of the total amount of the carrier, the mass fraction of the promoter metal component in terms of element is
0.5%-5%, wherein,
The alumina support of one or more of promoter metal components containing in IA, IIA, Group IVB is by one kind
Modified hydrated alumina through shaping, dry, roasting, promoter metal group is introduced in roasting article shaped using the method for dipping afterwards
Prepared by the method divide, dried and be calcined, the preparation method of the modified hydrated alumina includes：(1) at least one is hydrated oxygen
Change aluminium roasting, the roasting condition includes：Temperature is 200 DEG C -950 DEG C, and the time is -48 hours 0.5 hour；(2) by step (1)
Obtained product of roasting is mixed with least one boehmite and/or false boehmite and water, obtains a kind of mixture；
(3) mixture for obtaining step (2) is heated in closed reactor, and heating condition includes：Temperature is 60
DEG C -250 DEG C, the time is -48 hours 0.5 hour；(4) product for obtaining step (3) is dried；
Either, it is described to contain the aluminum oxide containing one or more of promoter metal components in IA, IIA, Group IVB
Carrier by a kind of modification hydrated alumina of one or more of promoter metal components containing in IA, IIA, Group IVB through into
It is prepared by type, drying, the method for roasting, wherein, the preparation method of the hydrated alumina containing adjuvant component of the modification includes：
(1) at least one hydrated alumina is calcined, the roasting condition includes：Temperature is 200 DEG C -950 DEG C, and the time is 0.5 small
When -24 hours；(2) product of roasting for obtaining step (1) and at least one boehmite and/or false boehmite, contain
Compound and the water mixing of promoter metal component, obtain a kind of mixture；(3) mixture for obtaining step (2) is closed
Heated in reactor, heating condition includes：Temperature is 60 DEG C -250 DEG C, and the time is -48 hours 0.5 hour；
(4) product for obtaining step (3) is dried.
2. the catalyst according to 1, it is characterised in that the promoter metal component be selected from lithium, sodium, potassium, magnesium, calcium, titanium and
The one or more of zirconium, on the basis of the total amount of the carrier, the mass fraction of the adjuvant component in terms of element is
0.5%-5%.
3. the catalyst according to 1, it is characterised in that it is soft that the hydrated alumina is selected from hibbsite, a false water
One or more in aluminium stone, boehmite.
4. the catalyst according to 1, it is characterised in that the one or more containing in IA, IIA, Group IVB are helped
The alumina support of agent metal component is by a kind of modified hydrated alumina through shaping, dry, roasting, the method that dipping is used afterwards
It is introduced on to roasting article shaped in the method for promoter metal component, drying and roasting, drying condition includes：Temperature is 60-300
DEG C, the time is 0.5-10 hours, and roasting condition includes：Temperature is 350-800 DEG C, and the time is 0.5-10 hours；It is described containing containing
The alumina support of one or more of promoter metal components in IA, IIA, Group IVB by one kind contain selected from IA, IIA,
The modification hydrated alumina of one or more of promoter metal components in Group IVB is through in shaping, the method dried, be calcined, drying
Condition includes：Temperature is 60-300 DEG C, and the time is 0.5-10 hours, and roasting condition includes：Temperature is 350-800 DEG C, and the time is
0.5-10 hours.
5. the catalyst according to 1, it is characterised in that the modified hydrated alumina or containing selected from IA, IIA, Group IVB
In one or more of promoter metal components modification hydrated alumina preparation method the step of (1) roasting condition include：
Temperature is 300 DEG C -750 DEG C, and the time is -24 hours 1 hour.
6. the catalyst according to 5, it is characterised in that described roasting condition includes：Temperature is 350 DEG C -650 DEG C, when
Between be -10 hours 2 hours.
7. the catalyst according to 1, it is characterised in that the modified hydrated alumina or containing selected from IA, IIA, Group IVB
In one or more of promoter metal components modification hydrated alumina preparation method the step of (3) heating condition bag
Include：Temperature is 60 DEG C -140 DEG C, and the time is 0.5-48 hours.
8. the catalyst according to 7, it is characterised in that described heating condition includes：Temperature is 80 DEG C -120 DEG C,
Time is 4-24 hours.
9. the catalyst according to 1, it is characterised in that the modified hydrated alumina or containing selected from IA, IIA, Group IVB
In one or more of promoter metal components modification hydrated alumina preparation method the step of (3) heating condition bag
Include：Temperature is that the time is 0.5-48 hours more than or equal to 140 DEG C to being less than or equal to 250 DEG C.
10. the catalyst according to 9, it is characterised in that described heating condition includes：Temperature is 150-220 DEG C,
Time is 4-24 hours.
11. the catalyst according to 1, it is characterised in that the modified hydrated alumina or containing selected from IA, IIA, IVB
The drying condition bag of the step of preparation method of the modification hydrated alumina of one or more of promoter metal components in race (4)
Include：Drying temperature is 80 DEG C -150 DEG C, and drying time is -12 hours 1 hour.
12. the catalyst according to 11, it is characterised in that described drying condition includes：Drying temperature is 80 DEG C -150
DEG C, drying time is -12 hours 1 hour.
13. the catalyst according to 1, it is characterised in that the modified hydrated alumina or containing selected from IA, IIA, IVB
In the step of preparation method of the modification hydrated alumina of one or more of promoter metal components in race (2) by step (1)
Obtained product of roasting and at least one boehmite or false boehmite, the compound containing adjuvant component do not conform to containing helping
In the mixture that the compound and water of agent component are mixed to get, solid content in mass is 1%-80%, wherein, the roasting
The mass ratio of product and the boehmite counted using butt or false boehmite is burnt as 0.1-20.
14. the catalyst according to 13, it is characterised in that the product of roasting for obtaining step (1) in the step (2)
With at least one boehmite or false boehmite, the compound containing adjuvant component or without containing adjuvant component and water
In the mixture being mixed to get, solid content in mass is 5%-70%, wherein, the product of roasting and one in terms of butt
The mass ratio of boehmite or false boehmite is 0.2-12.
15. the catalyst according to 1, it is characterised in that on the basis of the catalyst, carrier contains in the catalyst
Measure as 50-90 weight %, the content of group VIII metal component is 1-10 weight %, and the content of vib metals component is 5-
40 weight %.
16. the catalyst according to 15, it is characterised in that on the basis of the catalyst, carrier in the catalyst
Content be 60-85 weight %, the content of group VIII metal component is 1.5-6 weight %, the content of vib metals component
For 10-35 weight %.
17. a kind of hydrodeoxygenation process, is included under hydrogenation conditions, oxygen containing feed oil is contacted instead with catalyst
Should, it is characterised in that the catalyst is the catalyst described in 1-16 any one.
In the present invention, various easily operated shapings are can be made into depending on the different carriers required in catalyst of the present invention
Thing.For example, spherical, tablet and bar shaped.
Described shaping is carried out using customary way, such as tabletting, spin, extrusion method.Using customary way
During shaping, to ensure that the introducing auxiliary agent into material to be formed (modified hydrated alumina) that is smoothed out of shaping is allowed, example
Such as when extrusion, appropriate extrusion aid and water can be introduced into foregoing material to be formed, extrusion molding afterwards.The extrusion aid
Species and consumption may each be that this area is conventional, such as common extrusion aid can be selected from sesbania powder, methylcellulose, shallow lake
One or more in powder, polyvinyl alcohol, PVOH.The method of the drying and roasting be conventional method, for example, by it is described into
Type thing is dried using the method for heating, and drying condition includes：Drying temperature be 60-180 DEG C, preferably 80-150 DEG C, dry when
Between be 0.5-24 hours, preferably 1-12 hours.Described is roasted to conventional method, for example, the article shaped is placed in into Muffle
The method of kiln roasting, roasting condition includes：Sintering temperature is 200-950 DEG C, and preferably 300-750 DEG C, roasting time is
0.5-48 hours, preferably 1-24 hours.
The compound of the component containing promoter metal preferably their water soluble compound, the example bag of this compound
Include：Lithium nitrate, lithium acetate, lithium sulfate, Lithiagel, lithium chloride, sodium nitrate, sodium acetate, sodium sulphate, basic carbonate sodium, chlorine
Change sodium, potassium nitrate, potassium acetate, potassium sulfate, basic carbonate potassium, potassium chloride, magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate,
Magnesium chloride, calcium nitrate, calcium acetate, calcium sulfate, basic carbonate calcium, calcium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, metatitanic acid four
Butyl ester, zirconium nitrate, zirconyl nitrate and zirconium oxychloride etc..
When the alumina support of one or more of promoter metal components containing in IA, IIA, Group IVB is by one
Kind of modified hydrated alumina through shaping, dry, roasting, promoter metal is introduced in roasting article shaped using the method for dipping afterwards
When component, drying and the method preparation being calcined, it is introduced into being enough the compound by the component containing promoter metal in the carrier
On the premise of, described dipping method is not particularly limited, for example, can be impregnated using hole saturation or using excessive liquid method leaching
Stain.When described dipping is using excessive liquid method dipping, the step of generally also including as filtered, to remove excessive solvent.
Dip time is usually 0.1-24 hours, preferably 0.5-8 hours.
The step of drying and roasting to impregnation product are generally included in the dipping method, wherein, dry condition
Including：Temperature is preferably 60~120 DEG C, and the time is preferably 0.5~10 hour, and the condition of roasting includes：Temperature is preferably 350~
800 DEG C, more preferably 400~700 DEG C, roasting time is preferably 0.5~10 hour, more preferably 1~5 hour.
In the preparation method of modified hydrated alumina of the present invention, the hibbsite includes gibbsite
(α-Al2O3·3H2O), surge aluminium stone (β1-Al2O3·3H2) and promise diaspore (β O2-Al2O3·3H2O)。
The false boehmite is also known as boehmite, with X-ray diffraction characterize, be one kind at 14.5 ° ± 0.5 ° (2
θ) there is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse.
The boehmite is also known as boehmite, is characterized with X-ray diffraction, is that one kind goes out at 14.5 ° ± 0.5 ° (2 θ)
Now most strong, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and
55.2 ° respectively occur corresponding to (131), (220) and (151) crystal face false boehmite not available for diffraction maximum).
Inventors of the present invention have surprisingly found that, boehmite and/or false boehmite are passed through with one or more of
200 DEG C -950 DEG C are calcined (heat treatment) 0.5-24 hours, are preferably calcined (heat treatment) 1-24 hours through 300 DEG C -750 DEG C, enter one
Step is preferably through 350 DEG C -650 DEG C product of roastings for being calcined (heat treatment) 2-10 hours, the changes with or without the component containing promoter metal
After compound and water mixing, the mixture is heated 0.5-48 hours in closed container in 60 DEG C -250 DEG C, is preferable over
80-220 DEG C is heated 4-24 hours, thus obtains the boehmite and/or false boehmite of a kind of modification, a water
The relative crystallinity of softening aluminium stone and/or false boehmite is improved, and thus fired obtained aluminum oxide maintain it is higher
Specific surface area and pore volume.When preparing catalyst using the carrier thus prepared, catalyst performance is improved.
In described method of modifying, when control heat treatment temperature of the mixture in closed container for 140 DEG C with
When upper, gained modified product is boehmite；When controlling heat treatment temperature less than 140 DEG C, the crystalline phase of products therefrom is with rising
The crystalline phase of hydrated alumina in beginning raw material is consistent.
The product of roasting (aluminum oxide) and at least one hydrated alumina, the chemical combination with or without the component containing promoter metal
In thing and the mixture of water mixing, solid content in mass is 1%-80%, preferably 5%-70%, the roasting therein
The mass ratio of product and the hydrated alumina counted using butt is burnt as 0.1-20, preferably 0.2-12.
When the product of roasting and at least one hydrated alumina, the compound with or without the component containing promoter metal and
It is slurries (for example, solid content in mass is 1%- that water content in the mixture of water mixing, which is enough to make the mixture,
35%) when, the step of filtering is preferably included before the drying of (4) preferably the step of the preparation method of the modified hydrated alumina
Suddenly.
In a detailed embodiment, the aqua oxidation in the crystalline phase and initiation material of the modified product is preferably made
The heating condition of the consistent step (3) of the crystalline phase of aluminium includes：Temperature is 60 DEG C and is extremely less than 140 DEG C, and the time is 0.5-
48 hours；The heating condition of the further preferred step (3) includes：Temperature is 80-120 DEG C, and the time is that 1-24 is small
When.
In another embodiment, the step (3) that the modified product is boehmite is preferably made
Heating condition include：Temperature is that the time is 0.5-48 hours more than or equal to 140 DEG C to being less than or equal to 250 DEG C；Further
It is preferred that the heating condition of the step (3) include：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
It is to be prepared using arbitrary prior art, this is not particularly limited.
In the preparation method of modified hydrated alumina of the present invention, it is being enough the hydrated alumina 300
DEG C of -950 DEG C roastings (heat treatment) 1-24 hours, preferably through 300 DEG C of -750 DEG C of roastings (heat treatment) 1-24 hours, further preferably
Under conditions of being calcined (heat treatment) 2-10 hours through 350 DEG C -650 DEG C, the present invention is to the method for roasting described in step (1) without spy
Do not limit.For example, it may be the hydrated alumina is roasted in usual baking oven or roaster under air atmosphere
Burn.
The closed reactor can be the reactor of the arbitrarily achievable heating (hydro-thermal reaction), example
Such as, autoclave etc., the reaction can be carried out under static conditions, also carried out under stirring, preferably stir shape
Hydro-thermal process is carried out under state.
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 in 600 DEG C of constant temperature 4 hours, the weight of product and the oxidation before roasting after roasting
The percentage of the weight ratio of aluminium hydrate, the weight of the preceding hydrated alumina of weight ÷ roastings of product after butt=roasting
Amount × 100%.
In the present invention, counted by oxide and on the basis of the catalyst, the catalyst preferably comprises 50-90 weight %
Carrier, 1-10 weight % group VIII metal component, 5-40 weight % vib metals component；Further preferably urge
Agent contains 60-85 weight % carrier, 1.5-6 weight % group VIII metal component, 10-35 weight % vib
Metal component.
Wherein, the vib metals component is selected from molybdenum and/or tungsten, and group VIII metal component is selected from nickel and/or cobalt.
It is conventional method to the method for the carrier to load metal component, for example, it may be at least one the will be contained
VIII and at least one method for being configured to impregnate the carrier after mixed solution selected from vib metals compound；Can be with
It is that will individually prepare impregnated carrier after solution selected from vib metals compound containing at least one group VIII and at least one
Method.Wherein, by the regulation and control of the concentration of the solution to metallic components, consumption or carrier consumption, it can prepare
Go out the catalyst of specified content, this is that those skilled in the art are readily appreciated by.After the impregnation steps are completed,
It the step such as can optionally be dried, be calcined or not be calcined.The condition of the drying and roasting is conventional, for example, dry
Dry temperature is 100-300 DEG C, and preferably 100-280 DEG C, drying time is 1-12 hours, preferably 2-8 hours；Sintering temperature is
350-550 DEG C, preferably 400-500 DEG C, roasting time is 1-10 hours, preferably 2-8 hours.
One or more in the soluble compound of the group VIII metallic compound selected from these metals, for example,
Can be the one or more in the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
One or more in described soluble compound of the vib metals compound selected from these metals, for example,
Can be the one or more in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
The catalyst provided according to the present invention, needs in presence of hydrogen, by the catalyst and vulcanization before the use
Agent haptoreaction, reaction condition includes：140-400 DEG C of temperature, -15 MPas of pressure normal pressure；Described vulcanizing agent can be existing
Technology is arbitrarily enough to realize the material of the catalyst vulcanization, for example, the vulcanizing agent can be elemental sulfur and sulfur-bearing chemical combination
One or more in thing；Can also be one or more in elemental sulfur and sulfur-containing compound mixed with hydrogen and/or hydrocarbon ils
Compound.Described hydrocarbon ils can be the distillate for being suitable for catalyst vulcanization (for example, hexamethylene, direct steaming gasoline or straight run
Kerosene distillate oil etc.) or feedstock oil is in itself.The sulfur-containing compound includes inorganic sulfocompound (for example：Vulcanization
Hydrogen, ATS (Ammonium thiosulphate)) and organic sulfur compound is (for example：CS2Or organic sulfur compound (dimethyl disulfide (DMDS), dimethyl sulfide
(DMS), tert-butyl polysulfide (PSTB) and ethyl mercaptan) in one or more.In the oil plant containing sulfur-containing compound
The mass fraction for the sulfur-containing compound counted using sulphur is 0.1-15%, and the volume space velocity of the oil plant of sulfur-containing compound is 0.1-20h-1。
It is preferred that, the mass fraction for the sulfur-containing compound counted in the oil plant containing sulfur-containing compound using sulphur is 1-6%, sulfur-containing compound
Oil plant volume space velocity be 1-5h-1。
The vulcanization can carry out also In-situ sulphiding in device outside device.For example, the vulcanization in situ carried out in reactor：
Can be that S, H are directly injected into recycle hydrogen2S、CS2Or organic sulfur compound (dimethyl disulfide (DMDS), diformazan
Base thioether (DMS), tert-butyl polysulfide (PSTB) and ethyl mercaptan etc.) form the mixing of hydrogen and sulfur-containing compound
Gas, and the vulcanization carried out under the cited reaction conditions, the volume fraction for finally making hydrogen sulfide in the gaseous mixture are 0.5-15%,
The volume space velocity of gaseous mixture is 100-3000h-1；It is preferred that, the volume fraction of hydrogen sulfide is 3-10%, gaseous mixture in the gaseous mixture
Volume space velocity be 300-1000h-1。
In the present invention, the hydrogenation conditions are the usual condition that hydrogenation deoxidation reacts, for example, 140-400 DEG C of temperature,
- 15 MPas of pressure normal pressure；Hydrogen to oil volume ratio 100-1000；The volume space velocity 0.1-20h of the feedstock oil-1。
Compared with existing hydrogenation catalyst, the catalyst that the present invention is provided is with higher hydrogenation deoxidation activity and stably
Property.
For example, using the meta-xylene of carbon disulfide containing 0.03%- and 30% ortho-methyl phenol as reaction raw materials, to the present invention
The catalyst of offer and comparative catalyst carry out the active comparative evaluation of hydrogenation deoxidation, using the activity of comparative catalyst as 100, then originally
Invention provides the hydrogenation deoxidation activity of catalyst up to 119.Successive reaction after 8 hours the activity of comparative catalyst be reduced to 86, then
The hydrogenation deoxidation activity that the present invention provides catalyst is 117.Compared with existing catalyst, the catalyst hydrogenation that the present invention is provided takes off
Oxygen activity is higher, and stability is more preferable.
The catalyst that the present invention is provided is suitable for including DCL/Direct coal liquefaction generation oil, Fischer-Tropsch synthesis oil, oil shale and life
The hydrogenation deoxidation process of the oxygen containing feeds such as material oil oil.
Embodiment
The present invention is described further for the following examples.
Wherein, the measure reference of sample crystalline phase, relative crystallinity and mean grain size《Solid catalyst Practical Research side
Method》(Liu Weiqiao, Sun Gui big compile, Sinopec publishing house, 2000,57-89) and《Petrochemical Engineering Analysis method (RIPP experiment sides
Method)》X-ray diffraction method in (Yang Cuiding, Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405) is carried out.
The content of adjuvant component is determined using X-fluorescence method.
The hydrated alumina used in experiment is：
CL-A powder (false boehmite powder), is 100%, grain size 2.9nm, the weight of butt 70 with respect to relative crystallinity
% is measured, purchased from sinopec Chang Ling catalyst branch company.
CL-B powder (boehmite), relative crystallinity is 100%, grain size 5.2nm, the weight % of butt 78, is purchased from
Sinopec Chang Ling catalyst branch company).
CL-C powder (gibbsite (α-Al2O3·3H2O)), relative crystallinity is 100%, grain size 156nm, butt 65
Weight %, purchased from sinopec Chang Ling catalyst branch company.
10000 grams of CL-A 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 bar that circumscribed circle diameter is 1.6 millimeters.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere
Under in Muffle furnace 600 DEG C of constant temperature 4 hours, obtain alumina support CL-A-Al2O3.It is characterized by X-ray diffraction method brilliant
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, as a result arranges
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 bar that circumscribed circle diameter is 1.6 millimeters.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere
Under in Muffle furnace 600 DEG C of constant temperature 4 hours, obtain alumina support CL-B-Al2O3.It is characterized by X-ray diffraction method brilliant
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption determines its specific surface area and pore volume, as a result arranges
In table 2.
In the present invention, according to the modified hydrated alumina preparation method the step of (1) obtained product of roasting be：
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 to 600 DEG C, and in 600 DEG C of constant temperature within 4 hours.
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 to 450 DEG C, and in 450 DEG C of constant temperature within 4 hours.
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 to 400 DEG C, and in 400 DEG C of constant temperature within 4 hours.
CL-A-350：10000 grams of CL-A powder are weighed to be raised to 3 DEG C/min of heating rate in baking oven in a nitrogen atmosphere
350 DEG C, and obtain CL-A-350 within 4 hours in 350 DEG C of constant temperature.
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 to 600 DEG C, and in 600 DEG C of constant temperature within 4 hours.
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 to 450 DEG C, and in 450 DEG C of constant temperature within 4 hours.
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 to 400 DEG C, and in 400 DEG C of constant temperature within 4 hours.
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 to 350 DEG C, and in 350 DEG C of constant temperature within 4 hours.
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 4 hours in 600 DEG C of constant temperature.
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 6 hours in 450 DEG C of constant temperature.
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 6 hours in 400 DEG C of constant temperature.
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 6 hours in 350 DEG C of constant temperature.
Embodiment 1-10 illustrates boehmite and/or false boehmite prepared by method of modifying of the present invention, Yi Jiyou
The alumina support that the modifier is prepared.
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 and 3600 grams of deionized waters to be mixed into slurries；The slurries are transferred into band to stir
The volume mixed in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C, and constant temperature 4 under agitation
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified product Q-S1 is obtained.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
By Q-S1 banded extruder (manufacturers：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S1.Its crystalline 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 determines its specific surface area and pore volume, 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 with terms of butt
The mass ratio of CL-A powder is 1.34), they and 3600 grams of deionized waters to be mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S2 is obtained.Pass through X-ray
Diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S2 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, 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 with terms of butt
The mass ratio of CL-A powder is 4.25), they and 3600 grams of deionized waters to be mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；It is down to
Room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S3 is obtained.Pass through X-ray
Diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
Formed alumina and its preparation that the present invention is provided：
Q-S3 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, 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 and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be 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 are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；Room temperature and after filtering is down to, will
Filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S4.It is characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S4 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, 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 and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be 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 are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 60 DEG C of constant temperature 48 hours；Room temperature and after filtering is down to, will
Filter cake is dried 8 hours in 120 DEG C, obtains modified hydrated alumina Q-S5.It is characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S5 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, 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 and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be 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 are transferred into the volume with stirring
In the autoclave of stainless steel band polytetrafluoro liner, it is closed after be heated to 100 DEG C of constant temperature 24 hours；Room temperature and after filtering is down to,
Filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina Q-S6 is obtained.It is characterized by X-ray diffraction method
Crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S6 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, 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 for the CL powder counted using butt are as 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in autoclave of the volume with stirring for 5 liters of stainless steel band polytetrafluoro liner,
160 DEG C of constant temperature is heated to after closed 4 hours；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, obtained through changing
The hydrated alumina Q-S7 of property.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, as a result arranged
In table 1.
By Q-S7 banded extruder (manufacturers：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S7.Its crystalline 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 determines its specific surface area and pore volume, 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 for the CL powder counted using butt are as 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in autoclave of the volume with stirring for 5 liters of stainless steel band polytetrafluoro liner,
160 DEG C of constant temperature is heated to after closed 4 hours.It is down to after room temperature, high pressure kettle cover is opened, adds 11.75 grams of ammonium dihydrogen phosphates,
Room temperature continues to stir 24 hours, after filtering, filter cake is dried 8 hours in 120 DEG C, the modified oxygen containing auxiliary agent phosphorus is obtained
Change aluminium hydrate Q-S8.Its crystalline phase, relative crystallinity and grain size are characterized by X-ray diffraction method, table 1 is as a result listed in
In.
By Q-S8 banded extruder (manufacturers：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S8.Its crystalline 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 determines its specific surface area and pore volume, and the results are shown in Table 2.It is glimmering using X
Light method determines the content of adjuvant component, and the mass fraction for the phosphate builder counted using 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 with terms of butt
The mass ratio of CL-A powder is 1.34), they and 3600 grams of deionized waters to be mixed into slurries；The slurries are transferred to band
The volume of stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues to stir 24 hours, then filters.By filter cake through 120 DEG C
Dry 8 hours, obtain the modified hydrated alumina Q-S9 containing auxiliary agent titanium.It is characterized by X-ray diffraction method brilliant
Phase, relative crystallinity and grain size, the results are shown in Table 1.
Q-S9 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, the results are shown in Table 2.The content of adjuvant component, the titanium in terms of element are determined 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 and 3600 grams of deionized waters to be mixed into slurries；The slurries are transferred into band to stir
The volume mixed in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 200 DEG C, and constant temperature 4 under agitation
Hour；Afterwards, room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified product Q-S10 is obtained.It is logical
Cross X-ray diffraction method and characterize its crystalline phase, relative crystallinity and grain size, the results are shown in Table 1.
By Q-S10 banded extruder (manufacturers：South China Science ＆ Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into
Circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern bar.After wet bar is dried 4 hours through 120 DEG C, in air atmosphere in Muffle furnace
600 DEG C of constant temperature 4 hours, obtains alumina support S10.Its crystalline 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 determines its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 11-13 illustrate the present invention use boehmite is prepared by conventional method of modifying and/or a false water is soft
The modifier of aluminium stone and the alumina support prepared by the modifier.
Embodiment 11
470 grams of the CL-A powder in terms of butt is weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
The volume with stirring is transferred to in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-1 is obtained.
Its crystalline 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 bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S11 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.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, 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
Volume with stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；Drop
To room temperature and after filtering, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-2 is obtained.Pass through X-
Diffraction characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-2 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S12 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.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, the results are shown in Table 2.
Embodiment 13
470 grams of the CL-B powder in terms of butt is weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
The volume with stirring is transferred to in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 200 DEG C of constant temperature 4
Hour；Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, modified hydrated alumina QBF-3 is obtained.
Its crystalline 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 bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S13 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.Pass through N2Absorption/desorption is surveyed
Its fixed specific surface area and pore volume, the results are shown in Table 2.
Embodiment 14-25 illustrates the preparation of the carrier of offer of the present invention, the i.e. carrier containing auxiliary agent.
Embodiment 14
400 grams of alumina support S1 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, 2 are dried at 120 DEG C
Hour, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S1 of carrier containing auxiliary agent is obtained.It is described
Auxiliary agent content in carrier (on the basis of carrier) is listed in table 3.
Embodiment 15
400 grams of alumina support S2 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, 2 are dried at 120 DEG C
Hour, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S2 of carrier containing auxiliary agent is obtained.It is described
Auxiliary agent content in carrier (on the basis of carrier) is listed in table 3.
Embodiment 16
400 grams of alumina support S3 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, 2 are dried at 120 DEG C
Hour, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S3 of carrier containing auxiliary agent is obtained.It is described
Auxiliary agent content in carrier (on the basis of carrier) is listed in table 3.
Embodiment 17
400 grams of alumina support S4 are weighed, are impregnated 5 hours with the aqueous solution containing 27.32 gram of six calcium chloride hydrate, 120
DEG C dry 2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R- of carrier containing auxiliary agent is obtained
S4.Auxiliary agent content in the carrier (on the basis of carrier) is listed in table 3.
Embodiment 18
400 grams of alumina support S5 are weighed, with the aqueous solution containing 16.96 grams of lithium nitrates and 28.36 grams of magnesium nitrate hexahydrates
Dipping 5 hours, dries 2 hours at 120 DEG C, is finally warming up to 550 DEG C of constant temperature with 5 DEG C/min of heating rate and activates 4 hours,
Obtain the R-S5 of carrier containing auxiliary agent.Auxiliary agent content in the carrier (on the basis of carrier) is listed in table 3.
Embodiment 19
400 grams of alumina support S6 are weighed, with the water-soluble immersion containing 8.76 grams of sodium nitrate and 12.32 gram of six calcium chloride hydrate
Stain 5 hours, dries 2 hours at 120 DEG C, is finally warming up to 550 DEG C of constant temperature with 5 DEG C/min of heating rate and activates 4 hours, obtain
To the R-S6 of carrier containing auxiliary agent.Auxiliary agent content in the carrier (on the basis of carrier) is listed in table 3.
Embodiment 20
400 grams of alumina support S7 are weighed, with containing 4.76 grams of potassium nitrate, 12.36 grams of titanium sulfates and 10.31 gram of eight hydration oxygen
The aqueous solution of zirconium chloride impregnates 5 hours, is dried 2 hours at 120 DEG C, is finally warming up to 550 DEG C with 5 DEG C/min of heating rate
Constant temperature is activated 4 hours, obtains the R-S7 of carrier containing auxiliary agent.Auxiliary agent content in the carrier (on the basis of carrier) is listed in table 3.
Embodiment 21
400 grams of alumina support S10 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, in 120 DEG C of dryings
2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S10 of carrier containing auxiliary agent is obtained.Institute
The auxiliary agent content for stating in carrier (on the basis of carrier) is listed in table 3.
Embodiment 22
400 grams of alumina support S11 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, in 120 DEG C of dryings
2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S11 of carrier containing auxiliary agent is obtained.Institute
The auxiliary agent content for stating in carrier (on the basis of carrier) is listed in table 3.
Embodiment 23
400 grams of alumina support S12 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, in 120 DEG C of dryings
2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S12 of carrier containing auxiliary agent is obtained.Institute
The auxiliary agent content for stating in carrier (on the basis of carrier) is listed in table 3.
Embodiment 24
400 grams of alumina support S13 are weighed, are impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, in 120 DEG C of dryings
2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, the R-S13 of carrier containing auxiliary agent is obtained.Institute
The auxiliary agent content for stating in carrier (on the basis of carrier) is listed in table 3.
Embodiment 25
147 grams of 110 grams of 88 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 and the mass ratio of the CL-A powder in terms of butt of the powder of CL-A-350~600 be for 248 grams of powder, 178 grams of CL-A-600 powder
7.81), they are mixed with 3600 grams of deionized waters, and adds 51.12 grams of titanium sulfates, slurries are stirred into；The slurries are shifted
To the volume with stirring in the autoclave of 5 liters of stainless steel band polytetrafluoro liner, it is closed after be heated to 160 DEG C of constant temperature 4 hours；
Room temperature and after filtering is down to, filter cake is dried 8 hours in 120 DEG C, the hydrated alumina Q-S14 containing auxiliary agent is obtained.Pass through
X-ray diffraction method characterizes its crystalline phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S14 is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters with banded extruder (be the same as Example 1).Wet bar warp
After 120 DEG C of dryings 4 hours, 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain the R-S14 of carrier containing auxiliary agent in air atmosphere.It is logical
Cross X-ray diffraction method and characterize its crystalline phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption is determined
Its specific surface area and pore volume, the results are shown in Table 2.
Comparative example 1
Illustrate reference carrier containing auxiliary agent and preparation method thereof.
Weigh 400 grams of CL-A-Al2O3Alumina support, is impregnated 5 hours with the aqueous solution containing 15.86 grams of potassium nitrate, 120
DEG C dry 2 hours, 550 DEG C of constant temperature are finally warming up to 5 DEG C/min of heating rate and activated 4 hours, carrier containing auxiliary agent is obtained
DT-1.Auxiliary agent content in the carrier (on the basis of carrier) is listed in table 3.
Table 1
Wherein, when determining the crystallinity of false boehmite, using CL-A powder as standard specimen；Determining the knot of boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When determining gama-alumina crystallinity, with CL-B-Al2O3Thing standard specimen.
Table 2
| Embodiment | Aluminum oxide | Specific surface area, m2/g | Pore volume, cm3/g |
| CL-A-Al2O3 | 283 | 0.71 | |
| CL-B-Al2O3 | 201 | 0.51 | |
| 1 | S1 | 255 | 0.66 |
| 2 | S2 | 238 | 0.62 |
| 3 | S3 | 213 | 0.61 |
| 4 | S4 | 236 | 0.62 |
| 5 | S5 | 265 | 0.68 |
| 6 | S6 | 258 | 0.66 |
| 7 | S7 | 216 | 0.60 |
| 8 | S8 | 222 | 0.61 |
| 9 | S9 | 243 | 0.63 |
| 10 | S10 | 185 | 0.60 |
| 11 | S11 | 233 | 0.52 |
| 12 | S12 | 173 | 0.60 |
| 13 | S13 | 131 | 0.45 |
| 25 | R-S14 | 246 | 0.63 |
Table 3
Embodiment 26-37 illustrates the catalyst of the invention provided and its preparation.
Weigh R-S1, R-S2, R-S3, R-S4, R-S5, R-S6, R-S7, R- that 200 grams of embodiments 14~25 are prepared
S10, R-S11, R-S12, R-S13 and R-S14, respectively with the ammonia containing 24.53 grams of ammonium heptamolybdates, 15.85 grams of cabaltous nitrate hexahydrates
Then 209 milliliters of dippings of the aqueous solution, dip time 2 hours is dried 8 hours, 430 DEG C are calcined 4 hours, are catalyzed at 120 DEG C
Agent C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 and C12.
Comparative example 2-3 illustrates the preparation method of comparative catalyst.
Comparative example 1
Weigh support C L-A-Al2O3With each 200 grams of DT-1 carriers, prepared using method identical with embodiment 26-37
Catalyst D1 and D2.
Catalyst performance evaluation：
The hydrogenation deoxidation performance that embodiment 26-37 provides the comparative catalyst that catalyst and comparative example 2-3 are provided is evaluated,
As a result it is listed in table 4.Hydrogenation deoxidation reactivity worth appreciation condition is as follows：
Reaction is carried out in 30 milliliters of fixed bed reactors, and catalyst particle size is 16~18 mesh, and catalyst amount is 30ml.
Catalyst vulcanization, sulfurized oil is the hexamethylene containing 5% carbon disulfide, and vulcanization reaction condition includes：290 DEG C of temperature, vulcanizes oil body
Product air speed 2h-1Charging；Pressure 4MPa；Hydrogen to oil volume ratio 300,8 hours time.
After vulcanization terminates, adjustment reaction temperature is 300 DEG C, is passed through feedstock oil reaction.Feedstock oil is containing 0.03% curing
The meta-xylene of carbon and 30% ortho-methyl phenol.Reaction condition includes：Pressure 4.0MPa, volume space velocity 2h-1；Hydrogen to oil volume ratio
900。
This experiment analyzes product using offline sampling, starts sampling after 3 hours in stable reaction, then every 1 hour
A sample is taken, reaction continues 8 hours.With Agilent HP7890A gas-chromatographies, (hydrogen flameionization is detected obtained sample
Device, DB-Petro chromatographic columns) analyze.Using ortho-methyl phenol as model compound, the primary product of reaction is toluene, also
There is a small amount of hexahydrotoluene.The hydrogenation deoxidation conversion ratio of ortho-methyl phenol is calculated as follows：X=[(S0-St)/S0]×
100%, StFor the relative peak area of ortho-methyl phenol in product；S0For the relative peak of oxygenatedchemicals ortho-methyl phenol in raw material
Area.Hydrogenation deoxidation activity A is calculated as follows：In A=ln [100/ (100-X)], formula, X is hydrogenation deoxidation conversion ratio.Take contrast
The hydrogenation deoxidation activity of catalyst D1 ortho-methyl phenol is 100, then the relative ortho-methyl phenol hydrogenation deoxidation of other catalyst
Activity can be represented by the formula：Relative activity=(AQT/AD1A in) × 100%, formulaQTFor the activity of other catalyst, AD1For reference
The activity of catalyst.Specific reaction result is shown in Table 4.
Table 4
Shown by the result of table 4, it is active and steady to show higher hydrogenation deoxidation according to the hydrogenation catalyst of the present invention
It is qualitative.
Claims (17)
1. a kind of hydrogenation catalyst, contains the oxidation containing one or more of promoter metal components in the Ith A, II A, IV B races
Alumina supporter and load molybdenum selected from VIB races on this carrier and/or tungsten metal component and nickel selected from the VIIIth race and/or
Cobalt metal component, on the basis of the total amount of the carrier, the mass fraction for the promoter metal component counted using element is 0.5%-
5%, wherein,
The alumina support of one or more of promoter metal components containing in the Ith A, II A, IV B races is modified by one kind
Hydrated alumina through shaping, dry, roasting, afterwards using dipping method to introduce in roasting article shaped promoter metal component,
Prepared by the method dried and be calcined, the preparation method of the modified hydrated alumina includes：（1）By at least one hydrated alumina
Roasting, the roasting condition includes：Temperature is 200 DEG C -950 DEG C, and the time is -48 hours 0.5 hour；（2）By step（1）Obtain
Product of roasting mixed with least one boehmite and/or false boehmite and water, obtain a kind of mixture；（3）
By step（2）Obtained mixture is heated in closed reactor, and heating condition includes：Temperature be 60 DEG C-
250 DEG C, the time is -48 hours 0.5 hour；（4）By step（3）Obtained product is dried；
Either, it is described to contain the alumina support containing one or more of promoter metal components in the Ith A, II A, IV B races
By a kind of modification hydrated alumina of one or more of promoter metal components containing in the Ith A, II A, IV B races through being molded, doing
It is prepared by dry, roasting method, wherein, the preparation method of the hydrated alumina containing adjuvant component of the modification includes：（1）It is near
A kind of few hydrated alumina roasting, the roasting condition includes：Temperature is 200 DEG C -950 DEG C, and the time is 0.5 hour -24 small
When；（2）By step（1）Obtained product of roasting is with least one boehmite and/or false boehmite, containing adjuvant component
Compound and water mixing, obtain a kind of mixture；（3）By step（2）Obtained mixture is carried out in closed reactor
Heat, heating condition includes：Temperature is 60 DEG C -250 DEG C, and the time is -48 hours 0.5 hour；（4）By step（3）
Obtained product is dried.
2. catalyst according to claim 1, it is characterised in that the promoter metal component be selected from lithium, sodium, potassium, magnesium, calcium,
The one or more of titanium and zirconium, on the basis of the total amount of the carrier, the mass fraction of the adjuvant component in terms of element is
0.5%-5%。
3. catalyst according to claim 1, it is characterised in that the hydrated alumina is selected from hibbsite, vacation one
One or more in boehmite, boehmite.
4. catalyst according to claim 1, it is characterised in that described one kind or several containing in the Ith A, II A, IV B races
The alumina support for planting promoter metal component uses what is impregnated by a kind of modified hydrated alumina through being molded, drying, be calcined, afterwards
Method to roasting article shaped on is introduced into promoter metal component, drying and roasting method in, drying condition includes：Temperature is 60-
300 DEG C, the time is 0.5-10 hours, and roasting condition includes：Temperature is 350-800 DEG C, and the time is 0.5-10 hours；It is described to contain
Have the alumina support containing one or more of promoter metal components in the Ith A, II A, IV B races by one kind contain selected from the Ith A,
In method of the modification hydrated alumina of one or more of promoter metal components in II A, IV B races through being molded, drying, being calcined,
Drying condition includes：Temperature is 60-300 DEG C, and the time is 0.5-10 hours, and roasting condition includes：Temperature is 350-800 DEG C, when
Between be 0.5-10 hours.
5. catalyst according to claim 1, it is characterised in that the modified hydrated alumina or containing selected from the Ith A, II A,
The step of preparation method of the modification hydrated alumina of one or more of promoter metal components in IV B races（1）Roasting condition
Including：Temperature is 300 DEG C -750 DEG C, and the time is -24 hours 1 hour.
6. catalyst according to claim 5, it is characterised in that described roasting condition includes：Temperature is 350 DEG C -650
DEG C, the time is -10 hours 2 hours.
7. catalyst according to claim 1, it is characterised in that the modified hydrated alumina or containing selected from the Ith A, II A,
The step of preparation method of the modification hydrated alumina of one or more of promoter metal components in IV B races（3）Heating
Condition includes：Temperature is 60 DEG C -140 DEG C, and the time is 0.5-48 hours.
8. catalyst according to claim 7, it is characterised in that described heating condition includes：Temperature be 80 DEG C-
120 DEG C, the time is 4-24 hours.
9. catalyst according to claim 1, it is characterised in that the modified hydrated alumina or containing selected from the Ith A, II A,
The step of preparation method of the modification hydrated alumina of one or more of promoter metal components in IV B races（3）Heating
Condition includes：Temperature is that the time is 0.5-48 hours more than or equal to 140 DEG C to being less than or equal to 250 DEG C.
10. catalyst according to claim 9, it is characterised in that described heating condition includes：Temperature is 150-
220 DEG C, the time is 4-24 hours.
11. catalyst according to claim 1, it is characterised in that the modified hydrated alumina or containing selected from the Ith A, II A,
The step of preparation method of the modification hydrated alumina of one or more of promoter metal components in IV B races（4) drying condition
Including：Drying temperature is 80 DEG C -150 DEG C, and drying time is -12 hours 1 hour.
12. the catalyst according to claim 11, it is characterised in that described drying condition includes：Drying temperature be 80 DEG C-
150 DEG C, drying time is -12 hours 1 hour.
13. catalyst according to claim 1, it is characterised in that the modified hydrated alumina or containing selected from the Ith A, II A,
The step of preparation method of the modification hydrated alumina of one or more of promoter metal components in IV B races（2）In by step
（1）Obtained product of roasting and at least one boehmite or false boehmite, the compound containing adjuvant component are free of
In the mixture that compound and water containing adjuvant component are mixed to get, solid content in mass is 1%-80%, wherein, it is described
The mass ratio of product of roasting and the boehmite counted using butt or false boehmite is 0.1-20.
14. the catalyst according to claim 13, it is characterised in that the step（2）In by step（1）Obtained roasting
Product and at least one boehmite or false boehmite, the compound containing adjuvant component or without containing adjuvant component with
And in the mixture that is mixed to get of water, solid content in mass is 5%-70%, wherein, the product of roasting with terms of butt
The mass ratio of boehmite or false boehmite is 0.2-12.
15. the catalyst according to claim 1, it is characterised in that on the basis of the catalyst, is carried in the catalyst
The content of body is 50-90 weight %, and the content of metal component of group VIII is 1-10 weight %, the content of metal component of group VIB
For 5-40 weight %.
16. catalyst according to claim 15, it is characterised in that on the basis of the catalyst, in the catalyst
The content of carrier is 60-85 weight %, the content of metal component of group VIII is 1.5-6 weight %, and metal component of group VIB contains
Measure as 10-35 weight %.
17. a kind of hydrodeoxygenation process, is included under hydrogenation conditions, by oxygen containing feed oil and catalyst haptoreaction, its
It is characterised by, the catalyst is the catalyst described in claim 1-16 any one.
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| CN114522692B (en) * | 2020-10-30 | 2023-07-11 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and heavy oil hydrotreating method |
| CN113104857B (en) * | 2021-04-14 | 2022-09-30 | 吉林大学 | Low-temperature preparation method of transition metal boride |
| CN115888719A (en) * | 2022-10-31 | 2023-04-04 | 华南理工大学 | Magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258346A (en) * | 1992-07-13 | 1993-11-02 | United Catalysts Inc. | Nickel hydrogenation catalyst |
| CN1230520A (en) * | 1998-03-26 | 1999-10-06 | 中国石油化工总公司 | Preparation of alumina |
| CN101230289A (en) * | 2007-01-23 | 2008-07-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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2014
- 2014-07-18 CN CN201410345119.2A patent/CN105268449B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258346A (en) * | 1992-07-13 | 1993-11-02 | United Catalysts Inc. | Nickel hydrogenation catalyst |
| CN1230520A (en) * | 1998-03-26 | 1999-10-06 | 中国石油化工总公司 | Preparation of alumina |
| CN101230289A (en) * | 2007-01-23 | 2008-07-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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