CN106362758B - A kind of alkadienes selective hydrocatalyst and its application - Google Patents
A kind of alkadienes selective hydrocatalyst and its application Download PDFInfo
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Abstract
A kind of Hydrobon catalyst and its application, the Hydrobon catalyst contains carrier, the at least one non-noble metal components selected from group VIII of load on this carrier, at least one metal component and at least one selected from group VIB is selected from lithium, sodium, the alkaline components of potassium and Rubidium, it is characterized in that, it is counted by oxide and on the basis of catalyst, the non-noble metal components content of the group VIII is 0.5~8 weight %, the metal component content of the group VIB is 4~30 weight %, the alkaline components content is 1~7 weight %, the carrier is aluminium oxide, the aluminium oxide is made by a kind of hydrated alumina.Compared with prior art, hydrofinishing by hydrogenation dialkene removal for the purpose of of the catalyst provided by the invention to the alkadienes hydrogenation activity with higher and selectivity in gasoline fraction oil, particularly suitable for the gasoline fraction oil containing alkadienes.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and its applications, add more specifically to a kind of diene hydrocarbon-selective
Hydrogen catalyst and its application.
Background technique
In catalytically cracked gasoline contain more alkadienes, under certain reaction temperature, alkadienes except itself polymerization in addition to,
It can also react with hydro carbons other in catalytically cracked gasoline, generate colloid and other coking precursors, therefore be usually to adopt
It is removed with the method choice for adding hydrogen.
US6,255,548 discloses a kind of preparation to unsaturated hydro carbons such as alkynes and alkadienes selective hydrocatalyst
Method.The catalyst is supported on carrier by least one group VIII metal and at least one promoter metal M and is made.The VIII group
Metal can be one or more of nickel, palladium, platinum, rhodium, ruthenium, iridium, preferably palladium, nickel, platinum, 0.01~50 weight of content range
% is measured, if it is noble metal preferably 0.05~1 weight %, preferably 5~30 weight % if the metal is nickel.Metal M is selected from
One or more of germanium, tin, gold, silver, 0.01~10 weight % of metal M content range, preferably 0.02~5 weight %.This is urged
Agent can also contain the alkali metal (such as potassium or sodium) and/or 0.01~2.0 weight % elementary sulfur of 0.1~3 weight %.
US6,388,162 discloses a kind of method that alkadienes is removed in olefin feedstock.This method is to carbon number 10
~20 raw material rich in alkene is refined, and alkadienes therein is removed.The catalyst that this method uses is by alumina support
It is formed with the Metal Palladium being supported on the alumina support, 0.05~0.2 weight % of tenor, preferably 0.2 weight %, wherein
Alumina ratio surface area is not more than 15 meters2/ gram, preferably 2~5 meters2/ gram.
CN1302849A discloses a kind of Hydrogenation active protective agent and preparation method thereof, contains simultaneously in protective agent used carrier
There are gama-alumina and δ-aluminium oxide；3~the 22m% of metal oxide containing group vib and group VIII metal oxide in protective agent
0.5~5m%, the 0~2m% of element of race containing IA, the 0~3m% of element of race containing VA, 100~250m of specific surface2/ g, hole appearance 0.4~
0.8mL/g.Group vib metal oxide is the oxide of Mo, W in the protective agent, and group VIII metal oxide is Fe, Co, Ni
Oxide, VA race element be P, As, Sb, Bi element.The catalyst is suitable for the protection of catalyst for hydroprocessing of heavy oil
Agent uses.
CN1676580A discloses a kind of distillate method for removing alkadiene by selective hydrogenation, and this method is included in hydrofinishing
Under process conditions, distillate is contacted with catalyst, the catalyst contains a kind of alumina support and load on this carrier
Cobalt and/or nickel, molybdenum and/or tungsten and alkaline components, which is characterized in that the atomic ratio of the alkali metal and cobalt and/or nickel is
1.3~6.Hydrofining technology condition therein includes that reaction temperature is 160~300 DEG C, preferably 200~260 DEG C, hydrogen partial pressure
For 1.0~6.0 megapascal, preferably 1.2~4.0 megapascal, liquid hourly space velocity (LHSV) is 2.0~30.0 hours-1, it is preferably 5.0~20.0 small
When-1, hydrogen to oil volume ratio 50~600, preferably 100~400.
Summary of the invention
The technical problem to be solved in the present invention is to provide it is a kind of new, simultaneously there is the diene hydrocarbon-selective of greater activity to add
Hydrogen catalyst and its application method.To solve this technical problem, technical solution provided by the invention specifically includes：
A kind of Hydrobon catalyst contains carrier, load on this carrier at least one non-selected from group VIII
Noble metal component, at least one metal component and at least one alkali metal for being selected from lithium, sodium, potassium and Rubidium selected from group VIB
Component, which is characterized in that counted by oxide and on the basis of catalyst, the non-noble metal components content of the group VIII is
0.5~8 weight %, the metal component content of the group VIB are 4~30 weight %, and the alkaline components content is 1~7
Weight %, the carrier are aluminium oxide, and the aluminium oxide is made by a kind of modified hydrated alumina.
According to catalyst provided by the invention, the preparation of the modified hydrated alumina includes the following steps：It (1) will at least
A kind of hydrated alumina roasting, the roasting condition include：Temperature is 300~950 DEG C, and the time is 0.5~24 hour；(2)
The product of roasting that step (1) obtains is mixed at least one boehmite and/or false boehmite and water, obtains one
Kind mixture；(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include：
Temperature is 60~250 DEG C, and the time is 0.5~48 hour；(4) product for obtaining step (3) is dry, obtains the modified hydration
Aluminium oxide.
Under optimum condition：
The roasting condition of the step (1) includes：Temperature is 300~750 DEG C, and the time is 1~24 hour；The step
(1) roasting condition is more preferably：Temperature is 350~650 DEG C, and the time is 2~10 hours.
The product of roasting and at least one boehmite or false boehmite that the step (2) obtains step (1)
And in the mixture that is mixed to get of water, solid content in mass is 1~80%, wherein the product of roasting with butt
The mass ratio of the boehmite of meter or false boehmite is 0.1~20；Under the conditions of further preferably, the step (2) will
The mixture that the product of roasting and at least one boehmite or false boehmite and water that step (1) obtains are mixed to get
In, solid content in mass is 5~70%, wherein the product of roasting and the boehmite or a false water in terms of butt
The mass ratio of softening aluminium stone is 0.2~12.
The hydrothermal conditions of the step (3) include：Temperature is 60 DEG C to less than 140 DEG C, and the time is 0.5~48 small
When；The hydrothermal conditions of the step (3) are more preferably：Temperature is 80~120 DEG C, and the time is 4~24 hours.It is described
The hydrothermal conditions of step (3) can also be：Temperature is 140~250 DEG C, and the time is 0.5~48 hour；Further preferably
For：Temperature is 150~220 DEG C, and the time is 4~24 hours.
The drying temperature of the step (4) is 60~180 DEG C, and drying time is 0.5~24 hour；Further preferred condition
Under, the drying temperature of the step (4) is 80~150 DEG C, and drying time is 1~12 hour.
According to catalyst of the present invention, in preparing the modified hydration alumina process, oxygen described in step (1)
Change aluminium hydrate and is selected from one or more of boehmite, false boehmite, hibbsite；Under optimum condition,
The hibbsite is gibbsite.
According to catalyst of the present invention, auxiliary agent, the adjuvant component can be contained in the modified hydrated alumina
Selected from one or more of IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB, the adjuvant component is preferably selected from
One or more of fluorine, phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium；When helping in the modified hydrated alumina containing above-mentioned
When agent, include the steps that introducing adjuvant component into obtained modification hydrated alumina in the step (4), with the modified water
On the basis of closing aluminium oxide dry weight, the introduction volume of the adjuvant component makes the finally obtained modified hydration oxygen containing adjuvant component
Change in aluminium, the adjuvant component content is 0.1~10 weight %, and under optimum condition, the adjuvant component content is 0.3~5 weight
Measure %；Into obtained modification hydrated alumina, the method for introducing adjuvant component includes in the step (4)：Adjuvant component will be contained
Compound be configured to aqueous solution, the aqueous solution and modified hydrated alumina are mixed into slurries, is filtered and dries later,
The drying temperature is 60~180 DEG C, and preferably 80~150 DEG C, the time is 0.5~24 hour, preferably 1~12 hour.
Under optimum condition, in catalyst of the present invention, counted by oxide and on the basis of catalyst, the Section VIII
The content of the non-noble metal components of race is 1~5 weight %, and the metal component content of the group VIB is 5~20 weight %, institute
Stating alkaline components content is 1.5~5 weight %.
Under optimum condition, in catalyst of the present invention, the non-noble metal components of the group VIII be nickel and/or
Cobalt, the metal component of the group vib are molybdenum and/or tungsten, further preferably molybdenum, and the alkaline components are potassium.
According to catalyst of the present invention, wherein can also be containing a kind of or several in alcohol, organic acid and organic amine
The organic matter of kind, it is 200~1500 polyethylene glycol, diethylene glycol, butanediol that the alcohol, which is selected from ethylene glycol, glycerine, molecular weight,
One or more of, the organic acid is selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexane diamine tetrem
One or more of acid, citric acid, tartaric acid, malic acid, the organic amine are selected from ethylenediamine or EDTA and its ammonium salt；It is described
The non-noble metal components molar ratio of organic matter and group VIII is 0.5~2.5, preferably 1~2.
The present invention also provides a kind of distillate hydrogenation processing methods, including at hydrotreating reaction conditions, by raw material
It is oily to be contacted with catalyst of the present invention.
In a particular embodiment, the preparation of the modified hydrated alumina includes the following steps：(1) at least one is aoxidized
The roasting of aluminium hydrate, the roasting condition include：Temperature is 300~950 DEG C, and the time is 0.5~24 hour；(2) by step (1)
Obtained product of roasting is mixed at least one boehmite and/or false boehmite and water, obtains a kind of mixture；
(3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include：Temperature is 60
~250 DEG C, the time is 0.5~48 hour；(4) product for obtaining step (3) is dry, obtains the modified hydrated alumina.
Hydrated alumina described in step (1) is in hibbsite, false boehmite, boehmite
One or more.Wherein, the hibbsite includes gibbsite (α-Al2O3·3H2O), surge aluminium stone (β1-Al2O3·
3H2O) and promise diaspore (β2-Al2O3·3H2O).The vacation boehmite is also known as boehmite, with X-ray diffractometer
Sign, the hydrated alumina of (020) crystallographic plane diffraction peak of disperse to be a kind of wide in 14.5 ° ± 0.5 ° (2 θ) appearance.
The boehmite is also known as boehmite, with X-ray diffraction characterization, goes out to be a kind of at 14.5 ° ± 0.5 ° (2 θ)
Existing strongest, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and
55.2 ° occur corresponding to diffraction maximum not available for the false boehmite of (131), (220) and (151) crystal face respectively).
In the present invention, the boehmite, false boehmite and gibbsite can be commercially available commodity, can also be with
It is that this is not particularly limited using arbitrary prior art preparation.
Under the conditions of being enough the hydrated alumina being roasted (heat treatment), the present invention is to the roasting in step (1)
Firing method is not particularly limited.For example, it may be by the hydrated alumina in atmosphere in usual baking oven or roaster
It is roasted under atmosphere, is also possible in the baking oven or roaster of vacuum-pumping under vacuum conditions or is passed through inert gas item
It is carried out under part.When the roasting is passed through inert gas, the inert gas can be arbitrary the foot under the roasting condition
With the not oxygen-containing gas of gasification, such as can be selected from one of nitrogen, argon gas, helium, carbon dioxide and water vapour or several
Kind.Roasting condition includes：300~950 DEG C roasting (heat treatment) 1~24 hour, preferably through 300~750 DEG C roasting (heat at
Reason) 1~24 hour, further preferably through 350~650 DEG C roasting (heat treatment) 2~10 hours.
In step (2), product of roasting and at least one boehmite and/or the soft aluminium of a false water that step (1) is obtained
Stone and water mixing, obtain a kind of mixture.In a specific embodiment, in the mixture that step (2) obtains, in mass
Solid content is 1~80%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt
It is 0.1~20；Under the conditions of further preferably, the product of roasting and at least one water that the step (2) obtains step (1) are soft
In the mixture that aluminium stone or false boehmite and water are mixed to get, solid content in mass is 5~70%, wherein institute
The mass ratio for stating product of roasting and boehmite or false boehmite in terms of butt is 0.2~12.
Butt described in step (2) refers to：A certain amount of hydrated alumina is in air atmosphere in Muffle furnace
Be raised to 600 DEG C with 4 DEG C/min of heating rate, then 600 DEG C constant temperature 4 hours, after roasting the weight of product and roast before institute
The percentage of the weight ratio of hydrated alumina is stated, the alumina hydration before the weight ÷ of product is roasted after butt=roasting
Weight × 100% of object.
In step (3), the mixture that step (2) obtains is subjected to hydro-thermal process, hydro-thermal process item in closed reactor
Part includes：Temperature is 60~250 DEG C, and the time is 0.5~48 hour.
In the present invention, when controlling hydro-thermal process temperature is 140 DEG C or more, gained modified product is boehmite；Control
When hydro-thermal process temperature processed is less than 140 DEG C, crystal phase and the starting material of products therefrom are consistent.
In a specific embodiment, preferably make the crystal phase of the modified product and starting material consistent described
The hydrothermal conditions of step (3) include：Temperature is 60 DEG C to less than 140 DEG C, and the time is 0.5~48 hour；Preferably：Temperature
It is 80~120 DEG C, the time is 4~24 hours.
In another embodiment, preferably make the step (3) of the modified product boehmite
Hydrothermal conditions include：Temperature is 140~250 DEG C, and the time is 0.5~48 hour；Further preferably：Temperature is 150
~220 DEG C, the time is 4~24 hours.
Wherein, reactor closed described in step (3) can be arbitrary the reactor that the hydro-thermal reaction can be achieved,
For example, autoclave etc., the reaction can be to be carried out under static conditions, is also carried out under stirring, is preferably stirred
Hydro-thermal process is carried out under state.
Include by the dry condition being dried of product that step (3) obtains in the step (4)：Drying temperature be 60~
180 DEG C, drying time is 0.5~24 hour；Under the conditions of further preferably, the drying temperature of the step (4) is 80~150
DEG C, drying time is 1~12 hour.
When containing auxiliary agent in the modified hydrated alumina, step (4) further includes introducing into modified hydrated alumina
The method of auxiliary agent obtains the modification hydrated alumina containing adjuvant component.The adjuvant component be selected from IIIA, IVA, VA, VIIA,
One or more of IIA, IIB, IIIB, Group IVB, in fluorine preferably wherein, phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium
It is one or more of.By butt count described on the basis of the modification hydrated alumina containing adjuvant component, the auxiliary agent based on the element
The mass fraction of component is 0.1~10 weight %, preferably 0.3~5 weight %, further preferably 0.3~4 weight %.Institute
Stating the method that auxiliary agent is introduced into modified hydrated alumina can be conventional method, such as impregnate.The change of adjuvant component will be contained
It closes object and is configured to aqueous solution, which is mixed with modified hydrated alumina, mixture is obtained, then mixture is done
It is dry.When water content is enough to starch the mixture in the mixture that auxiliary compound aqueous solution and modified hydrated alumina are formed
When liquid (for example, solid content in mass is 35% or less), the step of filtering is preferably included before the drying of the step (4)
Suddenly.Hydrated alumina after drying can also be immersed in the compound containing adjuvant component to be configured in aqueous solution, then again
It is secondary that hydrated alumina is dried.
The compound containing adjuvant component, preferably their water soluble compound, such as：Hydrofluoric acid, ammonium fluoride, hydrogen fluorine
Sour ammonium, fluosilicic acid, ammonium fluosilicate, boric acid, ammonium borate, ammonium metaborate, tetraboric acid ammonium, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, phosphoric acid
Ammonium dihydrogen, boric acid, tetraboric acid ammonium, silica solution, silicon tetrachloride, ammonium fluosilicate and ethyl orthosilicate, magnesium nitrate, magnesium acetate, sulfuric acid
Magnesium, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, lanthanum nitrate, lanthanum carbonate, chlorine
Change lanthanum, cerous nitrate, cerous carbonate, cerium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, butyl titanate, zirconium nitrate, zirconyl nitrate
With zirconium oxychloride etc..
According to the present invention, prepared using the modification hydrated alumina being prepared through the above steps as carrier of the present invention
When catalyst, the modification hydrated alumina can be molding or non-molding, preferably to be modified hydrated alumina molding
Object is as carrier.When selecting modified water to close aluminium oxide molding as carrier, the forming method can be arbitrary existing
There is technology.For example, the forming method can be the forming method of extrusion, round as a ball, tabletting and their combination.For guarantee at
Type is gone on smoothly, and can introduce auxiliary agent into material (being herein the mixture of hydrated alumina and cellulose ether) at the time of molding
With water etc., for example, when using the molding of extrusion method, including by the hydrated alumina and cellulose ether and water, contain or not
It is mixed containing extrusion aid, then extrusion molding obtains wet bar, then is dried to obtain molding of the present invention.The auxiliary agent choosing
From starch, the starch can be arbitrary the powder being grinding to obtain by vegetable seeds, such as sesbania powder.Preferred forming method
For the method for extruded moulding.The drying condition includes：Temperature 60 C to less than 350 DEG C, drying time 1~48 hour, preferably
Temperature is 80~150 DEG C, and drying time is 1~15h, and further preferred temperature is 100~130 DEG C, and drying time is 2~10h.
The roasting condition includes：450 DEG C to less than 1200 DEG C of temperature, calcining time be 0.5~12 hour, preferably 550~
1100 DEG C, drying time is 4~8 hours.
It is introduced on carrier according to the present invention using the modification hydrated alumina being prepared through the above steps as carrier
At least one non-noble metal components selected from VIII group, at least one metal component and at least one selected from group vib are selected from
Lithium, sodium, potassium and Rubidium the methods of alkaline components be conventional method, the method preferably impregnated, such as hole saturation dipping, mistake
Measure liquid dipping and spray impregnating.Wherein, including dipping solution is prepared, for example, by being selected from least one group VIB gold containing described
Belong to the compound of the compound of component, the compound of non-noble metal components containing at least one group VIII or alkali metal containing component
Dipping solution is prepared respectively, and the method for impregnated carrier is distinguished with these dipping solutions；Either by being selected from least one containing described
The chemical combination of the metal component of kind of group VIB, the compound of metal component containing at least one group VIII and alkali metal containing component
Two or three of preparation in object is mixed with dipping solution, and the method for impregnated carrier is distinguished with these dipping solutions.When the leaching
When stain is step impregnation, to the sequence of the dipping solution impregnated carrier there is no limit.Then through it is dry or not dry, roast or
It does not roast, obtains the catalyst.
Although being not required, dry step is preferably included after dipping every time.The drying condition includes：Dry temperature
100~210 DEG C of degree, preferably 120~190 DEG C, drying time 1~6 hour, preferably 2~4 hours.
It is counted by oxide and on the basis of the catalyst, the dosage of each component makes the non-of group VIII in the catalyst
Noble metal component content is 0.5~8 weight %, and the metal component content of group VIB is 4~30 weight %, and alkaline components contain
Measure 1~7 weight %.It under optimum condition, is counted by oxide and on the basis of catalyst, the dosage of each component makes in the catalyst
The non-noble metal components content of group VIII is 1~5 weight %, and vib metals constituent content is 5~20 weight %, described
The content of alkaline components is 1.5~5 weight %.It is counted by oxide and on the basis of catalyst, the dosage of each component makes described
The non-noble metal components content of group VIII is more preferably 1.5~5 weight % in catalyst, and vib metals component contains
Amount is more preferably 10~20 weight %.
The compound of the non-noble metal components containing VIII group is selected from one of their soluble-salt and complex compound
Or it is several, for example, one or more of the nitrate of group VIII metal, chloride, acetate, subcarbonate, with cobalt salt
For one or more of selected from cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and soluble-salt of cobalt.
The compound of the metal component containing group vib is selected from their one or more of soluble compound, for example,
Molybdenum oxide, molybdate (for example, ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate), tungstates are (for example, ammonium tungstate, ammonium metatungstate, secondary tungsten
One or more of sour ammonium, ethyl metatungstate).
The compound of the alkali metal containing, one or more of hydroxide preferably wherein, inorganic or acylate.
Such as potassium hydroxide, potassium nitrate, potassium chloride, potassium acetate, potassium phosphate, potassium hydrogen phosphate and biphosphate in potassium-containing compound
One or more of potassium.
In the preferred embodiment, the non-noble metal components of the group VIII be nickel and/or cobalt, further preferably
Cobalt；The metal component of the group vib is molybdenum and/or tungsten, further preferably molybdenum.
According to catalyst provided by the invention, also containing one in alcohol, organic acid and organic amine in preferred catalyst
Kind or several organic matters, the alcohol can be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight be 200~1500),
One or more of diethylene glycol, butanediol, the organic acid are selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-
One or more of cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid, the organic amine be selected from ethylenediamine or
EDTA and its ammonium salt.Wherein, the introduction volume selected from alcohol, organic acid and organic amine meets the organic matter and group VIII gold
The molar ratio for belonging to component is preferably 0.5~2.5, and further preferably 1~2.
When in the catalyst also containing the components such as organic matter one or more of in alcohol, organic acid and organic amine
When, the introducing method of one or more of organic matter in alcohol, organic acid and organic amine can be arbitrary method, such as
It can be by the compound containing the organic matter and the non-noble metal metal salt selected from VIII group, selected from the metal of group vib
The method that one or more of salt and alkali metal-containing compound are configured to impregnate after mixed solution the carrier introduces.
According to catalyst provided by the invention, wherein the catalytic of catalyst can be provided containing any present invention that do not influence
Can substance or can improve catalyst provided by the invention catalytic performance substance.Phosphorus can such as be contained, based on the element and with
On the basis of catalyst, the content of above-mentioned auxiliary agent is no more than 10 weight %, preferably 0.5~5 weight %.
When, also containing timesharing is organized selected from phosphorus etc., the introducing method selected from components such as phosphorus, which can be, appoints in the catalyst
The method of meaning, such as can be by containing the auxiliary agent compound be selected from VIII group non-noble metal metal salt and be selected from
The method for being configured to impregnate after mixed solution the carrier of the metal salt of group vib introduces.
Catalyst provided by the invention is before the use, it is usually preferred in presence of hydrogen, in 140~370 DEG C of temperature
Lower to carry out presulfurization with sulphur, hydrogen sulfide or containing sulfur feedstock, this presulfurization can carry out also In-situ sulphiding in device, general outside device
It is converted into sulfide type.
When catalyst provided by the invention is used for hydrotreating reaction, the hydrotreating reaction can be in arbitrary fraction
It is realized in oily hydrofining reaction device, this present invention is not particularly limited.The reaction condition of the hydrofinishing can basis
Raw material oil nature and requirement to oil quality adjust in following ranges：180~350 DEG C of reaction temperature, volume space velocity 3~
15h-1, 0.8~5.0MPa of hydrogen partial pressure, hydrogen to oil volume ratio 50~800.
Compared with prior art, catalyst provided by the invention is with higher to the alkadienes in gasoline fraction oil adds hydrogen
Activity and selectivity add hydrogen essence for the purpose of hydrogenation dialkene removal particularly suitable for the gasoline fraction oil containing alkadienes
System.The gasoline fraction can be catalytically cracked gasoline, coker gasoline, direct steaming gasoline, pressure gasoline etc..
Specific embodiment
The present invention will be further described for the following examples, but does not answer therefore understands that for limitation of the invention.It is real
Agents useful for same is except as expressly described chemically pure reagent in example.
Embodiment 1-10 illustrates that can be used for preparing the present invention provides carrier and its preparation of catalyst.
The measurement reference of sample crystal phase, relative crystallinity and mean grain size《Solid catalyst Practical Research method》(Liu
The big volume of Wei Qiao, Sun Gui, Sinopec publishing house, 2000,57-89) and《Petrochemical egineering analysis method (RIPP test methods)》(poplar
Kingfisher is fixed, and Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405) in X-ray diffraction method carry out.
Hydrated alumina used in experiment is：
CL-A powder (false boehmite powder), relative crystallinity 100%, grain size 2.9nm, 70 weight % of butt,
Purchased from middle petrochemical industry Chang Ling catalyst branch.
CL-B powder (boehmite), relative crystallinity 100%, grain size 5.2nm, 78 weight % of butt are purchased from
Middle petrochemical industry Chang Ling catalyst branch).
CL-C powder (gibbsite (α-Al2O3·3H2O)), relative crystallinity 100%, grain size 156nm, butt 65
Weight % is purchased from middle petrochemical industry Chang Ling catalyst branch.
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 item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere
Under in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-A-Al2O3.Its crystalline substance is characterized by X-ray diffraction method
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, as a result arranges
In table 2.
10000 grams of CL-B powder are weighed, with banded extruder (manufacturer：South China Science & Engineering University's science and technology industry head factory, model：F-
26 (III)) it is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere
Under in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-B-Al2O3.Its crystalline substance is characterized by X-ray diffraction method
Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, as a result arranges
In table 2.
It is according to the product of roasting that the step (1) prepared in modified hydrated alumina method in the present invention obtains：
CL-A-600：10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-A-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
CL-A-450：10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 3 DEG C/min of heating rate liter
CL-A-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
CL-A-400：10000 grams of CL-A powder are weighed in a nitrogen atmosphere in Muffle furnace with 5 DEG C/min of heating rate liter
CL-A-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
CL-A-350：10000 grams of CL-A powder are weighed to be raised in a nitrogen atmosphere with 3 DEG C/min of heating rate in baking oven
350 DEG C, and CL-A-350 is obtained within constant temperature 4 hours at 350 DEG C.
CL-B-600：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.
CL-B-450：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.
CL-B-400：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.
CL-B-350：10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter
CL-B-350 is obtained within constant temperature 4 hours to 350 DEG C, and at 350 DEG C.
CL-C-600：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 600 DEG C, and obtains CL-C-600 within constant temperature 4 hours at 600 DEG C.
CL-C-450：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 450 DEG C, and obtains CL-C-450 within constant temperature 6 hours at 450 DEG C.
CL-C-400：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 400 DEG C, and obtains CL-C-400 within constant temperature 6 hours at 400 DEG C.
CL-C-350：10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed
Rate is raised to 350 DEG C, and obtains CL-C-350 within constant temperature 6 hours at 350 DEG C.
Embodiment 1
120 grams of 350 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of A powder is 0.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 160 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S1.It is logical
It crosses X-ray diffraction method and characterizes its crystal phase, relative crystallinity and grain size, the results are shown in Table 1.
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 outside
Connect the cloverleaf pattern item that circular diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S1.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Embodiment 2
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S2.By X-ray diffraction side
Method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 3
Weigh respectively in terms of butt 464 grams of 109 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 4.25), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to
Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S3.By X-ray diffraction side
Method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
Q-S3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 4
150 grams of 100 grams of 84 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 250 grams of powder, 180 grams of CL-A-600 powder
8.10) they and 3600 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S4.Its crystal phase, opposite is characterized by X-ray diffraction method
Crystallinity and grain size, the results are shown in Table 1.
Q-S4 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 5
200 grams of 100 grams of 140 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A- in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 450 300 grams of powder, 10 grams of CL-A-600 powder
4.36) they and 3100 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 60 DEG C of constant temperature are heated to after closed 48 hours；It is down to room temperature and after filtering, it will
Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S5.Its crystal phase, opposite is characterized by X-ray diffraction method
Crystallinity and grain size, the results are shown in Table 1.
Q-S5 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 6
100 grams of 200 grams of 70 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively
(total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 400 grams of powder, 20 grams of CL-A-600 powder
10.29) they and 3200 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring,
In the autoclave of stainless steel band polytetrafluoro liner, 100 DEG C of constant temperature are heated to after closed 24 hours；It is down to room temperature and after filtering,
Filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S6.Its crystal phase, phase are characterized by X-ray diffraction method
To crystallinity and grain size, the results are shown in Table 1.
Q-S6 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Embodiment 7
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220
Gram, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder
(total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters,
160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it is modified
Hydrated alumina Q-S7.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result listed in table 1
In.
By Q-S7 banded extruder (manufacturer：South China Science & Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into outside
Connect the cloverleaf pattern item that circular diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S7.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
Embodiment 8
60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively
Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220
Gram, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder
(total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionized waters
It is mixed into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters,
160 DEG C of constant temperature are heated to after closed 4 hours.It is cooled to room temperature, high pressure kettle cover is opened, 11.75 grams of ammonium dihydrogen phosphates are added,
Room temperature continues stirring 24 hours, after filtering, filter cake is 8 hours dry in 120 DEG C, obtains the modification aqua oxidation of the phosphorus containing auxiliary agent
Aluminium Q-S8.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, 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 outside
Connect the cloverleaf pattern item that circular diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S8.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method
Size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.It is glimmering using X
Light method measures the content of adjuvant component, and the mass fraction of the phosphate builder based on the element is 0.41%.
Embodiment 9
Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt
The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band
In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours.It is down to
After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues stirring 24 hours, then filters.By filter cake through 120 DEG C
It is 8 hours dry, obtain the modification hydrated alumina Q-S9 of the titanium containing auxiliary agent.Its crystal phase, opposite is characterized by X-ray diffraction method
Crystallinity and grain size, the results are shown in Table 1.
Q-S9 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.The content of adjuvant component, the titanium based on the element are measured using X-fluorescence method
The mass fraction of auxiliary agent is 3.12%.
Embodiment 10
320 grams of 230 grams of CL-B powder, CL-A-450 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively
The mass ratio of B powder is 1.39), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir
In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 200 DEG C are heated to after closed, and constant temperature 4 under stiring
Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S10.
Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.
By Q-S10 banded extruder (manufacturer：South China Science & Engineering University's science and technology industry head factory, model：F-26 (III)) it is extruded into
The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace
600 DEG C constant temperature 4 hours, obtain alumina support S10.Its crystal phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method
Grain size, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.
The oxidation that comparative example 1-3 illustrates the modified hydrated alumina of reference method and prepared by the hydrated alumina
Aluminium.
Comparative example 1
470 grams of CL-A powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 160 DEG C of constant temperature 4 is heated to after closed
Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-1.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-1 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support D1 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Comparative example 2
470 grams of CL-A-600 powder are weighed, it is mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to
In the autoclave for the stainless steel band polytetrafluoro liner that volume with stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；Drop
It is to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-2.Spread out by X-ray
Shooting method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support D2 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
Comparative example 3
470 grams of CL-B powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries
It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 200 DEG C of constant temperature 4 is heated to after closed
Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-3.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.
QBF-3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp
120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support D3 in air atmosphere.Pass through X-
Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N2Absorption/desorption measurement
Its specific surface area and Kong Rong, the results are shown in Table 2.
The modified hydration alumina precursor crystal phase of table 1, relative crystallinity and grain size characterization
Wherein, when measuring the crystallinity of false boehmite, using CL-A powder as standard specimen；In the knot of measurement boehmite
When crystalline substance is spent, using CL-B powder as standard specimen；When measuring gama-alumina crystallinity, with CL-B-Al2O3Object standard specimen.
The modified hydration alumina ratio surface area of table 2 and hole hold characterization
Can be illustrated by 2 result of table, compared with prior art, the present invention be used to prepare the catalyst carrier have compared with
High specific surface area and biggish Kong Rong.
Embodiment 11-15 and comparative example 4 illustrate the preparation of catalyst provided by the invention and reference catalyst respectively.
Embodiment 11
100 grams of carrier Ss 5 are taken, 9.9 grams of ammonium molybdate, potassium hydroxide 3.3g, 10.8 grams of nickel nitrate are weighed, using 16 weight %
NH3Aqueous dissolution is made into 100 milliliters of maceration extract.100 grams of carrier Ss 5 are impregnated with this solution, dipping is after 4 hours, in 120 DEG C
4 hours dry, 350 DEG C roast 4 hours, obtain catalyst C1.Nickel, molybdenum, alkali metal content are listed in Table 3 below in catalyst C1.
Comparative example 4
100 grams of carrier D1 are taken, 9.9 grams of ammonium molybdate, potassium hydroxide 3.3g, 10.8 grams of nickel nitrate are weighed, using 16 weight %
NH3Aqueous dissolution is made into 100 milliliters of maceration extract.100 grams of carrier D1 are impregnated with this solution, dipping is after 4 hours, in 120 DEG C
4 hours dry, 350 DEG C roast 4 hours, obtain catalyst DB1.Nickel, molybdenum content are listed in Table 3 below in catalyst DB1.
Embodiment 12
100 grams of carrier Ss 5 are taken, 14.8 grams of ammonium molybdate, potassium hydroxide 4.8g are weighed, using the NH of 16 weight %3Aqueous solution is molten
Solution, is made into 100 milliliters of maceration extract.100 grams of carrier Ss 5 are impregnated with this solution, dipping is 4 hours dry in 180 DEG C after 4 hours, and 350
DEG C roasting 4 hours.Weigh 6.7 grams of basic nickel carbonate, EDTA13.5 grams, using the NH of 16 weight %395 milliliters of aqueous solution is again
Dipping, and it is 4 hours dry in 120 DEG C, obtain catalyst C2.The molar ratio of EDTA and group VIII metal component in catalyst C2
Value is 1.0 (for calculated value, similarly hereinafter), and nickel, molybdenum, alkali metal content are listed in Table 3 below in catalyst C2.
Embodiment 13
100 grams of carrier Ss 5 are taken, potassium hydroxide 6.5g is weighed, using aqueous dissolution, are made into 100 milliliters of maceration extract.Use this
Solution impregnates 100 grams of carrier Ss 5, and dipping is 4 hours dry in 180 DEG C after 4 hours, and 350 DEG C roast 4 hours.It is aoxidized with containing three
19.3 grams of molybdenum, 9.6 grams of basic nickel carbonate, 95 milliliters of the aqueous solution that 13.8 grams of citric acid impregnates again, and small in 140 DEG C of dryings 4
When, obtain catalyst C3.The molar ratio of citric acid and group VIII metal component is 1.0 in catalyst C3, in catalyst C3
Nickel, molybdenum, alkali metal content are listed in Table 3 below.
Embodiment 14
100 grams of carrier Ss 5 are taken, 24.0 grams of ammonium molybdate, potassium hydroxide 5.6g are weighed, using the NH of 16 weight %3Aqueous solution is molten
Solution, is made into 100 milliliters of maceration extract.100 grams of carrier Ss 5 are impregnated with this solution, dipping is 4 hours dry in 180 DEG C after 4 hours, and 350
DEG C roasting 4 hours.With containing 8.2 grams of basic cobaltous carbonate, 95 milliliters of the aqueous solution that 13.6 grams of citric acid impregnates again, and in 140
DEG C dry 4 hours, obtain catalyst C4.The molar ratio of citric acid and group VIII metal component is 1.0 in catalyst C4, is urged
Cobalt, molybdenum, alkali metal content are listed in Table 3 below in agent C4.
Embodiment 15
100 grams of carrier Ss 1 are taken, weigh 14.9 grams of ammonium molybdate, 5.2 grams of potassium hydroxide, using the NH of 16 weight %3Aqueous solution
Dissolution, it is to be dissolved to 14.3 grams of cobalt nitrate of investment after clear, it is made into 103 milliliters of maceration extract.100 grams of loads are impregnated with this solution
Body S1, dipping is 4 hours dry in 180 DEG C after 4 hours, and 350 DEG C roast 4 hours, obtains catalyst C5.Cobalt in catalyst C5,
Molybdenum, alkali metal content are listed in Table 3 below.
Active metal and alkali metal content in 3 catalyst of table
Note：Tenor is catalyst XRF analysis result after 550 DEG C roast 4 hours.
Embodiment 16-20
Embodiment 16-20 illustrates that the present invention provides the alkadienes selective hydrogenation performance that catalyst is used for gasoline fraction oil.
Using catalytically cracked gasoline heavy distillate as raw material (its property is shown in Table 4), evaluated on 50mL fixed-bed reactor
Catalyst C1~C5.Before formal charging, first catalyst is vulcanized with the direct steaming gasoline containing 2 weight % carbon disulfide, sulphur
Change condition is：1.6 megapascal of hydrogen partial pressure, 290 DEG C of temperature, liquid hourly space velocity (LHSV) 2h-1, hydrogen to oil volume ratio 300, vulcanization time 9 hours, later
Incision raw material reacted, reaction temperature be 160~180 DEG C, hydrogen partial pressure be 1.6 megapascal, volume space velocity 8 hours-1, hydrogen-oil ratio
(volume) 400, sampling analysis after reaction 100 hours, is as a result listed in table 5.
4 raw material oil nature of table
The measuring method of diene value：5 milliliters of samples are accurately drawn with pipette in ground conical flask, then quasi- with pipette
20 milliliters of benzene-anhydrous maleic acid anhydride solution (containing 30 grams of anhydrous maleic acid acid anhydrides in every liter of benzene) and 0.2 milliliter of iodo- diformazan is really added
Benzole soln (0.1N), while replacing sample to make blank test with 10 milliliters of benzene.Conical flask is loaded into spherical reflux condenser, is put into
It flows back 30 minutes in 80 DEG C of waters bath with thermostatic control, then from condenser 5 ml deionized waters of addition suitable for reading, continues reflux 30 minutes, make to remain
Remaining maleic anhydride is fully hydrolyzed.It is cooled to room temperature, rinses condenser with 5 milliliters of ether, 20 ml deionized waters respectively, then unload
Inferior pyramidal bottle.Mixture in bottle is poured into 250 milliliters of separatory funnels and is separated.Finally dripped with the sodium hydroxide solution of 0.5N
Aqueous solution after fixed separation, record consumption volume.
Diene value=12.692 × N × (B-A) L × d
In formula：N is NaOH concentration of standard solution；
B is the volume of NaOH solution consumed by blank test, milliliter；
A is the volume of NaOH solution consumed by sample, milliliter；
L is volume of sample, milliliter；
D is 20 DEG C of density of sample, grams per milliliter；
The measuring method of bromine valency is RIPP66-90.
Comparative example 5
This comparative example illustrates hydrofinishing performance of the reference catalyst for gasoline fraction oil.Using with embodiment 15-18
Same procedure evaluates comparative example catalyst DB1, and reaction result is shown in Table 5.
5 evaluating catalyst result of table
Table 5 the result shows that, with the prior art provide catalyst compared with, adding at hydrogen according to catalyst provided by the invention
When managing feedstock oil containing alkadienes, there is higher hydrogenation dialkene removal activity and selectivity.
Claims (23)
1. a kind of Hydrobon catalyst, contain carrier, load on this carrier at least one non-expensive selected from group VIII
Metal component, at least one metal component selected from group VIB and at least one alkali metal group selected from lithium, sodium, potassium and Rubidium
Point, which is characterized in that it is counted by oxide and on the basis of catalyst, the non-noble metal components content of the group VIII is 0.5 ~
8 weight %, the metal component content of the group VIB are 4 ~ 30 weight %, and the alkaline components content is 1 ~ 7 weight %, described
Carrier is aluminium oxide, and the aluminium oxide is made by a kind of modified hydrated alumina；Wherein, the preparation of the modified hydrated alumina
Including：（1）At least one hydrated alumina is roasted, the roasting condition includes：Temperature is 300 ~ 950 DEG C, the time 0.5
~ 24 hours；（2）By step（1）Obtained product of roasting and at least one boehmite and/or false boehmite and water
Mixing, obtains a kind of mixture；（3）By step（2）Obtained mixture carries out hydro-thermal process in closed reactor, at hydro-thermal
Manage bar part includes：Temperature is 60 ~ 250 DEG C, and the time is 0.5 ~ 48 hour；（4）By step（3）Obtained product is dry, obtains institute
State modified hydrated alumina.
2. catalyst according to claim 1, which is characterized in that the step（1）Roasting condition include：Temperature is
300 ~ 750 DEG C, the time is 1 ~ 24 hour.
3. catalyst according to claim 2, which is characterized in that the step（1）Roasting condition include：Temperature is
350 ~ 650 DEG C, the time is 2 ~ 10 hours.
4. catalyst according to claim 1, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It is 60 DEG C to less than 140 DEG C, the time is 0.5 ~ 48 hour.
5. catalyst according to claim 4, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It is 80 ~ 120 DEG C, the time is 4 ~ 24 hours.
6. catalyst according to claim 1, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It is 140 ~ 250 DEG C, the time is 0.5 ~ 48 hour.
7. catalyst according to claim 6, which is characterized in that the step（3）Hydrothermal conditions include：Temperature
It is 150 ~ 220 DEG C, the time is 4 ~ 24 hours.
8. catalyst according to claim 1, which is characterized in that the hydrated alumina is selected from boehmite, vacation
One or more of boehmite, hibbsite.
9. catalyst according to claim 8, which is characterized in that the hibbsite is gibbsite.
10. catalyst according to claim 1, which is characterized in that the step（2）By step（1）Obtained roasting produces
In the mixture that object and at least one boehmite or false boehmite and water are mixed to get, solid content in mass
It is 1 ~ 80%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.1 ~
20。
11. catalyst according to claim 10, which is characterized in that the step（2）By step（1）Obtained roasting produces
In the mixture that object and at least one boehmite or false boehmite and water are mixed to get, solid content in mass
It is 5 ~ 70%, wherein the mass ratio of the product of roasting and boehmite or false boehmite in terms of butt is 0.2 ~
12。
12. catalyst according to claim 1, which is characterized in that the step（4）Drying temperature be 60 ~ 180 DEG C,
Drying time is 0.5 ~ 24 hour.
13. catalyst according to claim 12, which is characterized in that the step（4）Drying temperature be 80 ~ 150 DEG C,
Drying time is 1 ~ 12 hour.
14. catalyst according to claim 1, which is characterized in that contain auxiliary agent in the modified hydrated alumina, it is described
Adjuvant component is selected from one or more of IIIA, IVA, VA, VIIA, IIA, IIB, IIIB, Group IVB, the step（4）Middle packet
The step of adjuvant component is introduced into obtained modification hydrated alumina is included, using the modified hydration alumina dry base weight amount as base
Standard, the introduction volume of the adjuvant component make in the finally obtained modification hydrated alumina containing adjuvant component, the adjuvant component
Content is 0.1 ~ 10 weight %.
15. catalyst according to claim 14, which is characterized in that the adjuvant component choosing in the modified hydrated alumina
From one or more of fluorine, phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium, it is with the modified hydration alumina dry base weight amount
Benchmark, the introduction volume of the adjuvant component make in the finally obtained modification hydrated alumina containing adjuvant component, the auxiliary agent group
Dividing content is 0.3 ~ 5 weight %.
16. catalyst according to claim 14 or 15, which is characterized in that the step（4）It is middle to obtained modified water
Closing the method that adjuvant component is introduced in aluminium oxide includes：Compound containing adjuvant component is configured to aqueous solution, by the aqueous solution
Slurries are mixed into modified hydrated alumina, is filtered and dries later, the drying temperature is 60 ~ 180 DEG C, and the time is
0.5 ~ 24 hour.
17. catalyst according to claim 16, which is characterized in that the drying temperature be 80 ~ 150 DEG C, the time be 1 ~
12 hours.
18. catalyst according to claim 1, which is characterized in that counted by oxide and on the basis of catalyst, described
The non-noble metal components content of VIII group is 1 ~ 5 weight %, and the metal component content of the group VIB is 5 ~ 20 weight %, described
The content of alkaline components is 1.5 ~ 5 weight %.
19. catalyst according to claim 1, which is characterized in that the non-noble metal components of the group VIII be nickel and/
Or cobalt, the metal component of the group vib are molybdenum/or tungsten, the alkaline components are potassium.
20. catalyst according to claim 19, which is characterized in that the non-noble metal components of the group VIII are cobalt,
The metal component of the group vib is molybdenum.
21. catalyst according to claim 1, which is characterized in that contain selected from alcohol, organic acid and have in the catalyst
The non-noble metal components of the organic matter of one or more of machine amine, the organic matter and the group VIII based on the element are rubbed
You are than being 0.5 ~ 2.5.
22. catalyst according to claim 21, which is characterized in that the alcohol is selected from ethylene glycol, glycerine, molecular weight and is
One or more of 200 ~ 1500 polyethylene glycol, diethylene glycol, butanediol, the organic acid are selected from acetic acid, maleic acid, grass
One or more of acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid, it is described to have
Machine amine is selected from ethylenediamine or EDTA and its ammonium salt, the non-noble metal components of the organic matter and the group VIII based on the element
Molar ratio be 1 ~ 2.
23. a kind of distillate hydrogenation processing method, including at hydrotreating reaction conditions, feedstock oil is contacted with catalyst,
It is characterized in that, the catalyst is catalyst described in claim 1 ~ 22 any one.
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| CN115672329A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | Co series eggshell type catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258346A (en) * | 1992-07-13 | 1993-11-02 | United Catalysts Inc. | Nickel hydrogenation catalyst |
| CN1368939A (en) * | 1999-08-11 | 2002-09-11 | 阿克佐诺贝尔公司 | Process for preparation of quasi-crystalline boehmites from inexpensive precursors |
| CN1631526A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
| CN103386310A (en) * | 2012-05-10 | 2013-11-13 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of dialkene and preparation and application thereof |
| CN104437523A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Dialkene selective hydrogenation catalyst, and preparation and application thereof |
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| EP1976631A2 (en) * | 2006-01-17 | 2008-10-08 | ExxonMobil Research and Engineering Company | Selective catalysts for naphtha hydrodesulfurization |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258346A (en) * | 1992-07-13 | 1993-11-02 | United Catalysts Inc. | Nickel hydrogenation catalyst |
| CN1368939A (en) * | 1999-08-11 | 2002-09-11 | 阿克佐诺贝尔公司 | Process for preparation of quasi-crystalline boehmites from inexpensive precursors |
| CN1631526A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
| CN103386310A (en) * | 2012-05-10 | 2013-11-13 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of dialkene and preparation and application thereof |
| CN104437523A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Dialkene selective hydrogenation catalyst, and preparation and application thereof |
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