CN105148909B - A kind of loaded catalyst and its preparation and application for hydrocarbon hydrocracking - Google Patents
A kind of loaded catalyst and its preparation and application for hydrocarbon hydrocracking Download PDFInfo
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Abstract
A kind of loaded catalyst of hydrocracking reaction for hydro carbons, counted on the basis of the weight of the loaded catalyst, the loaded catalyst includes 0.01 3 weight % platinum, the tungstic acid of 0.01 5 weight, and the carrier of surplus, the carrier are the carriers of the oxide comprising silicon and aluminium.The method that the hydrocracking reaction of hydro carbons is carried out the invention further relates to the preparation method of the loaded catalyst and using the loaded catalyst.
Description
Technical field
The present invention relates to hydrocarbon catalytic hydrocracking process, in particular it relates to which a kind of urge for carrying out hydro carbons
Change the loaded catalyst and its preparation and application of hydrocracking reaction.
Background technology
F- T synthesis technology also into gas to liquid technology (GTL), using synthesis gas as raw material urging in predominantly Fe-series catalyst
Synthesis obtains the liquid fuel product based on paraffin hydrocarbon under the conditions of change, is the technology effectively using coal and natural gas.China is
Country more than the few coal of one oil, once national energy security faces test, external crude oil can not be transported in time again, and this is from coal
To gas, then can be to play vital effect by the fischer-tropsch technologies of gas to liquid.On the other hand, with environmental problem day increasingly
Play, the heavy hydrocarbon changed into by F- T synthesis technology by coal has low-sulfur compared with the heavy hydrocarbon refined from oil, low
The advantages such as nitrogen, low arene content, it can effectively alleviate the problem of environmental pollution.
But the product hydrocarbonaceous that Fiscber-Tropscb synthesis technique obtains can not be straight as from the heavy petroleum hydrocarbon of Petroleum refining
Connect and be used as fuel oil, its main component is the complex mixture of hydro carbons and a small amount of oxygenatedchemicals containing C4-C70, and feature is
Linear paraffin content is more, chilling process more have more than 40% wax generation, although gained light wax oil Cetane number more than 70, by
Too high in its condensation point pour point, cold flow properties are too poor, it is difficult to are directly used as transporting fuel oil, it is necessary to will using mild hydrogenation process
Long linear wax oil cuts into midbarrel, keeps higher Cetane number while improving its cold flow properties, could so produce
Go out high-quality jet fuel, diesel fuel or various mediation fuel.
It is obvious that as last process that oils product (CTL or GTL) is prepared using coal or natural gas as raw material, add
The selectivity of hydrogen cracking process midbarrel directly determines the economic feasibility of whole technical process.But due to Fiscber-Tropscb synthesis
Hydrocarbon is mostly straight-chain hydrocarbons, and molecular weight is big, and the carbon-to-carbon bond strength of long-chain saturated hydrocarbons is more average, and difference is not notable, makes catalysis
Agent difficulty in chain rupture selectivity is larger, and the liquid oil that hydrocracking process obtains at present is often selectively less than 90%, condensation point
It is higher, while there are about surpassing the generation of 10% gas low-carbon hydro carbons, leverage the economic feasibility of whole technique.
Therefore, the carbon with needed for that the hydrocarbon product that F- T synthesis obtains obtains in being hydrocracked how is improved as far as possible
The yield of chain length, become the most important ring for influenceing whole F- T synthesis Technical Economy.
Hydrogenation component for the bifunctional catalyst of hydrocracking process has a hydrogenolysis hydrogenation activity, generally use tungsten,
The noble metal such as the base metals such as nickel, aluminium, cobalt or palladium, platinum, and its acidic components has cracking and isomerization activity as carrier, often
A small amount of molecular sieve and layer aluminium silicate or magnesium silicate etc. is added to form with alumina silicate, molecular sieve, alumina silicate.
At present in correlative study at home and abroad, hydrocracking process technology and catalyst research mostly concentrate notice
It is less for the hydrocracking process and catalyst research of F- T synthesis hydrocarbon in being hydrocracked for petroleum heavy hydrocarbon.However, due to
Obvious difference be present in itself component of F- T synthesis hydrocarbon and petroleum hydrocarbon, can not directly by the hydrocracking refined technique of petroleum hydrocarbon and
Catalyst is directly covered with F- T synthesis hydrocarbon.For example, one of two kinds of heavy hydrocarbons it is important be not both sulfur content difference, if
Directly widely used sulphided state ni-loaded catalyst in heavy petroleum hydrocarbon is used for be catalyzed the very low F- T synthesis hydrocarbon of sulfur content,
Not only result is not so good as outside people's will in midbarrel selectivity, and its catalytic activity can also be greatly reduced.
Problem to be solved by this invention is on the basis for the catalytic activity for ensureing F- T synthesis hydrocarbon hydrocracking catalyst
On, and can improves the selectivity of the midbarrel with required carbon chain lengths.Therefore, the invention provides one kind specifically for taking
The hydrocarbon for asking synthetic reaction to obtain carries out highly effective hydrogenation cracking, so as to prepare the method for the midbarrel with required carbon chain lengths,
This method is included in the auxiliary agent using composite noble metal platinum-tungsten-amorphous silicon Al catalysts and one or more kinds of Organic Alcohol/acid
Under conditions of so that F- T synthesis hydrocarbon is hydrocracked, and obtains the higher diesel component of selectivity.
The content of the invention
According to the first aspect of the invention, there is provided a kind of loaded catalyst, with the weight of the loaded catalyst
Counted on the basis of amount, the loaded catalyst includes 0.01-3 weight % platinum, 0.01-5 weight % tungstic acid, Yi Jiyu
The carrier of amount, the carrier are the carriers of the oxide comprising silicon and aluminium.
According to an embodiment of the invention, counted on the basis of the weight of the loaded catalyst, the support type
The content of platinum is 0.1-0.8 weight %, preferably 0.2-0.4 weight % in catalyst；The content of tungstic acid is 0.1-4.5 weights
Measure %, preferably 2-3 weight %；Surplus is carrier.
According to another implementation of the invention, the silica alumina ratio in the carrier is SiO2:Al2O3=0.1-10, preferably
0.5-5, more preferably 0.8-3.2, more preferably 1.2-2.0, most preferably 1.5-1.7；The carrier, which also optionally includes to be derived to cover, to be taken off
The component and molecular sieve of stone, are counted on the basis of the gross weight of the carrier, and the content of the component from montmorillonite is 5-30
Weight %, the content of the molecular sieve is 5-20 weight %.
The second aspect of the invention provides a kind of method for preparing loaded catalyst of the present invention, should
Method comprises the following steps：
I) preparation process of carrier：By amorphous silicon oxide, amorphous alumina, colloidal alumina binder and colloid oxygen
SiClx binding agent and optional montmorillonite and molecular sieve mix, and are molded, calcining, so as to prepare carrier；
Ii) tungsten load step：The carrier is impregnated with the solution comprising tungsten, obtains required tungsten load amount, so
After calcined；
Iii) platinum load step：The carrier is impregnated with the solution comprising platinum, obtains required platinum load capacity, so
After calcined；
Iv) in-situ activation step：The carrier for having loaded tungsten and platinum is heated in a hydrogen atmosphere；
Wherein described step ii) and step iii) order include situations below：Step ii is carried out first), then carry out
Step iii)；Or step iii is carried out first), then carry out step ii)；Or step ii) and step iii) carry out simultaneously.
According to an embodiment of the invention, for the preparation process of i) carrier, amorphous silicon oxide, amorphous
Aluminium, montmorillonite, molecular sieve, the weight ratio of colloidal alumina binder and colloidal silica silicon bonding are：
Amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina binder:Colloidal silica glues
Tie agent=1:(0.5-3.0):(0.3-1.6):(0.6-1.5):(0.6-1.5):(0.6-1.5)；
Preferably, the weight ratio is amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina glues
Tie agent:Colloidal silica silicon bonding=1:(1.3-2.5):(0.7-1.2):(0.8-1.2):(0.8-1.2):(0.8-1.2)；
Most preferably, the weight ratio is amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina
Binding agent:Colloidal silica silicon bonding=1:2:0.8:1:1:1.
According to another implementation of the invention, i) preparation process of carrier carries out in the following manner：Will be amorphous
Silica, amorphous alumina, montmorillonite, molecular sieve, colloidal alumina binder and colloidal silica silicon bonding mix,
The solid slurry that solids content is 50-80 weight % is formed, kneading and compacting is carried out to it, then at 60-150 DEG C, preferably 100-
0.5-20 hours, preferably 10-12 hours are dried at a temperature of 120 DEG C, then in 500-800 DEG C, preferably 600-650 DEG C of temperature
Lower roasting 0.5-10 hours, preferably 3-4 hours, obtain the carrier.
According to another implementation of the invention, the step is carried out in the following way：
Ii) tungsten load step is carried out in the following manner：Carrier is put into dipping 6-10 hours, institute in the aqueous solution of tungstenic
The concentration for stating tungsten in the aqueous solution of tungstenic is 0.1-0.5 mol/Ls, then by the solid after dipping at 450-600 DEG C, preferably
1-5 hours, preferably 2-4 hours, more preferably 3-3.5 hours are calcined at a temperature of 480-550 DEG C, more preferably 500-520 DEG C；
Iii) platinum load step is carried out in the following manner：Will be by step ii) carrier that is handled is in the water-soluble of platinum
6-10 hours are impregnated in liquid, the concentration of platinum is 0.01-0.05 mol/Ls in the aqueous solution of the platiniferous, then by after dipping
Solid is at 450-600 DEG C, preferably 480-550 DEG C, and 1-5 hours, preferably 2-4 hours are calcined at a temperature of more preferably 500-520 DEG C,
More preferably 3-3.5 hours；
Iv) the in-situ activation step is carried out in the following manner：By step iii) obtained product in a nitrogen atmosphere,
0.5-4 hours are dried at a temperature of 100-150 DEG C, preferably 120-140 DEG C, 2-2.5 hours are preferably dried, then in hydrogen gas
Under atmosphere, at 300-500 DEG C, 2-5 hours are heated at a temperature of preferably 350-450 DEG C, more preferably 400-420 DEG C, are obtained described negative
Supported catalyst.
The third aspect of the invention provides a kind of method being hydrocracked to hydro carbons, and this method includes：
Under conditions of it loaded catalyst and auxiliary agent be present, hydrocarbon raw material is hydrocracked；
The loaded catalyst loaded catalyst of the present invention, or pass through method system of the present invention
Standby loaded catalyst；
The auxiliary agent is one or more straight or brancheds, saturation or undersaturated C12-C20Aliphatic monobasic alcohol and/or
Aliphatic monoacid.
According to a preferred embodiment of the present invention, the hydrocarbon raw material is product made from F- T synthesis, comprising more
Kind is selected from saturation or unsaturation, the C of straight or branched1-C70Hydrocarbon, preferably C4-C70The hydro carbons of hydrocarbon, and the oxidation production of optional hydrocarbon
Thing；Counted on the basis of the weight of the hydrocarbon raw material, the content of the auxiliary agent is 0.5-3 weight %；The auxiliary agent is selected from following
One or more：Straight or branched, saturation or undersaturated C12 aliphatic monobasic alcohols, straight or branched, saturation or unsaturation
C14 aliphatic monobasic alcohols, straight or branched, saturation or undersaturated C16 aliphatic monobasic alcohols, straight or branched, saturation or
Undersaturated C18 aliphatic monobasic alcohols, straight or branched, saturation or undersaturated C12 Aliphatic monoacids, straight or branched,
Saturation or undersaturated C14 Aliphatic monoacids, straight or branched, saturation or undersaturated C16 Aliphatic monoacids, straight chain or
Side chain, saturation or undersaturated C18 Aliphatic monoacids；Preferably, the auxiliary agent is selected from following one or more：Bay
Alcohol, laurate, cardanol, myristic acid, palmityl alcohol, palmitic acid, stearyl alcohol, stearic acid.
According to another preferred embodiment of the present invention, being hydrocracked for the hydrocarbon raw material is entered in the following manner
OK：The loaded catalyst is placed in reaction vessel, the mixture of hydrocarbon raw material and auxiliary agent is introduced to institute in a gaseous form
State in reactor, while introduce hydrogen into the reactor, so that hydrocracking reaction occurs for the hydrocarbon raw material；
The reaction condition of the reaction is as follows：Temperature in reaction vessel is 360-380 DEG C；The volume of the hydrocarbon raw material is empty
Speed is 0.5-1.0h-1；Hydrogen Vapor Pressure in the reaction vessel is maintained at 5-8MPa；Using the weight of the hydrocarbon raw material as 100
Weight % is counted, and the dosage of auxiliary agent is 0.8-3 weight %, preferably 1.0-2.0 weight %；Input the hydrogen of the reaction vessel
The ratio between the volume of gas and hydrocarbon raw material normal temperature volume used, i.e. hydrogen-oil ratio are 1000-1500.
According to another implementation of the invention, in method of the present invention, catalysis of the present invention is used
The hydro carbons that agent is hydrocracked is Synthin made from fischer-tropsch reaction technique, and sulfur content therein is substantially less than petroleum fractionating
The hydro carbons that technique obtains.According to an embodiment of the invention, the sulfur content for the hydro carbons being hydrocracked in the present invention
Less than 500ppm, either less than 400ppm or less than 300ppm, either less than 200ppm or less than 100ppm, or it is low
In 80ppm, either less than 50ppm or less than 20ppm, either less than 10ppm or less than 5ppm；And the present invention urge
The hydro carbons that agent can constantly be catalyzed the low sulfur content carries out hydrocracking reaction, without carrying out frequently reactivation behaviour
Make.According to an embodiment of the invention, catalyst of the invention is urged above-mentioned low sulfur content hydrocarbon hydrocracking reaction
At least one day, preferably at least five days, more preferably at least one week, more preferably at least 15 days can be kept by changing activity, more preferably extremely
Few one month, more preferably at least two months, more preferably at least three months, so-called " holding catalytic activity " is represented using the present invention's
Catalyst carry out catalytic reaction when, with starting when feed stock conversion and specific product selectively compared with, on it experienced
After stating the time, the fall of feed stock conversion and specific product selectivity is more excellent no more than 20%, preferably more than 10%
Choosing is no more than 5%.
Embodiment
In the present invention, unless otherwise indicated, the ratio of all solids or liquid substance represents weight ratio, owns
The ratio of gaseous matter represent volume ratio, the proportional units of component are mol/L in all solution.
" scope " disclosed herein is in the form of lower and upper limit.Can be respectively one or more lower limits, and one
Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower and upper limit limit
The border of special scope is determined.All scopes that can be defined by this way are included and can be combined, i.e., any lower limit
It can combine to form a scope with any upper limit.For example, listing 60-120 and 80-110 scope for special parameter, manage
The scope solved as 60-110 and 80-120 is also what is expected.If in addition, the minimum zone value 1 and 2 listed, and if list
Maximum magnitude value 3,4 and 5, then following scope can all expect：1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, number range " a-b " represents the contracting of any real combinings between a to b
Sketch form shows that wherein a and b are real numbers.Such as number range " 0-5 " represents all to have listed herein between " 0-5 "
Whole real numbers, " 0-5 " are that the breviary of these combinations of values represents.
If be not specifically stated, the term " two kinds " used in this specification refers to " at least two ".
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and the side of being preferable to carry out
Formula can be mutually combined to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical scheme is formed to be mutually combined.
In the present invention, if without particularly illustrating, all steps mentioned in this article can be carried out sequentially, can also
It is random to carry out, it is preferred that being that order is carried out.For example, methods described includes step (a) and (b), represent that methods described can wrap
The step of order is carried out (a) and (b) are included, the step of order is carried out (b) and (a) can also be included.For example, described mention the side
Method may also include step (c), represent that step (c) can be added to methods described with random order, for example, methods described can include
Step (a), (b) and (c), step (a), (c) and (b) are may also comprise, step (c), (a) and (b) etc. can also be included.
In the present invention, if without particularly illustrating, " comprising " mentioned in this article represents open or envelope
Enclosed.For example, the " comprising " can represent that the other elements do not listed can also be included, it can also only include the member listed
Part.
In the present invention, " hydrocarbon " or " hydro carbons " represents the compound that is made up of carbon and hydrogen, can include saturation or unsaturation,
Straight or branched, alkane, alkene and the alkynes with various degrees of unsaturation.
The Catalyst And Method of the present invention is primarily directed to mix products made from fischer-tropsch reaction in the prior art.At this
Wen Zhong, product made from fischer-tropsch reaction are selected from saturation or unsaturation, the C of straight or branched comprising a variety of1-C70Hydrocarbon, preferably C4-C70
Hydrocarbon, the mixture of any one or more more preferably in the various hydro carbons with following carbon number：C1、C2、C3、C4、C5、C6、
C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、C22、C23、C24、C25、C26、
C27、C28、C29、C30、C31、C32、C33、C34、C35、C36、C37、C38、C39、C40、C41、C42、C43、C44、C45、
C46、C47、C48、C49、C50、C51、C52、C53、C54、C55、C56、C57、C58、C59、C60、C61、C62、C63、C64、
C65、C66、C67、C68、C69、C70.Product made from the fischer-tropsch reaction also optionally includes the oxidation product of these hydrocarbon, example
Such as alkylene oxide, alcohol, aldehyde, acid.According to an embodiment of the invention, on the basis of the gross weight of the fischer-tropsch reaction product
To count, the content of C1-C10 hydrocarbon is that the content of 0.1-1 weight %, C11-C20 hydrocarbon is 5-15 weight % in the fischer-tropsch reaction product,
The content of C21-C30 hydrocarbon is that the content of 30-45 weight %, C31-C40 hydrocarbon is that the content of 30-40 weight %, C41-C50 hydrocarbon is
The content of 25-35 weight %, C51-C60 hydrocarbon is that the content of 5-10 weight %, C60+ hydrocarbon is 0.1-5 weight %, other hydro carbons oxygen
The content for changing product is 0.01-0.1 weight %, and the summation of all components content is 100 weight %.Under normal conditions, Fischer-Tropsch
The hydro carbons with longer carbon chain length accounts for significant percentage in reaction product, it is therefore desirable to which the product after F- T synthesis is entered again
Row is hydrocracked, and in order to obtain the fuel product with required composition and quality as much as possible, it is desirable to generate as far as possible
More C10-C22 hydro carbons, and low molecular weight hydrocarbons, such as the selectivity of product of C1-C4 hydro carbons are reduced as far as possible.In addition, though
Inventor in specific examples below mainly with fischer-tropsch reaction product being hydrocracked illustrate the present invention various advantages, but
It is that Catalyst And Method of the invention may also be used for other hydrocarbon mixtures, such as Petroleum refining or other chemical industry synthesis techniques
Obtained hydrocarbon mixture carry out it is same be hydrocracked, and obtain essentially identical effect.And it is on the other side, this area is existing
Being hydrocracked for fischer-tropsch reaction product is then not used to for the catalyst that petroleum chemicals are hydrocracked, and is obtained gratifying
Effect.
According to certain embodiments of the present invention, hydrogenation is carried out to fischer-tropsch reaction product in the catalyst using the present invention to split
After change, the conversion ratio of fischer-tropsch reaction product hydrocarbon is not less than 70 weight %, preferably not less than 72 weight %, preferably not less than 75 weights
%, more desirably not less than preferably not less than 75 weight %, more desirably not less than 78 weight %, 80 weight % are measured, it is more preferably not low
In 82 weight %, more desirably not less than 85 weight %, more desirably not less than 90 weight %, more desirably not less than 93 weight %, more
Preferably not less than 95 weight %.According to certain embodiments of the present invention, fischer-tropsch reaction is produced in the catalyst using the present invention
After thing is hydrocracked, the selectivity of C10-C22 hydrocarbon is not less than 50 weight %, preferably not less than 52 weights in products therefrom
%, more desirably not less than preferably not less than 54 weight %, preferably not less than 56 weight %, 58 weight % are measured, more desirably not less than
60 weight %, more desirably not less than 62 weight %, more desirably not less than 64 weight %, more desirably not less than 66 weight %, it is more excellent
Choosing is not less than 67 weight %, more desirably not less than 70 weight %, more desirably not less than 72 weight %.According to some realities of the present invention
Mode is applied, after being hydrocracked using the catalyst of the present invention to fischer-tropsch reaction product, C1-C4 hydrocarbon in products therefrom
Selectivity is not higher than 10 weight %, preferably no greater than 8 weight %, preferably no greater than 7 weight %, preferably no greater than 6.8 weight %,
More preferably no higher than 6.5 weight %, more preferably no higher than 6.2 weight %, more preferably no higher than 6.0 weight % are not more preferably high
In 5.9 weight %, more preferably no higher than 5.7 weight %, more preferably no higher than 5.5 weight %, more preferably no higher than 5.2 weights
Measure %, more preferably no higher than more preferably no higher than 5 weight %, 4.7 weight %.
The present invention develops a kind of bifunctional catalyst, and the catalyst is oxide carried in carrier by noble metal platinum and tungsten
On, hydrogenation/dehydrogenation activity is provided by the synergy of noble metal platinum and tungsten oxide, it is possible thereby to improve dual-functional hydrogenation cracking
The transformation in planta rate of catalyst.According to an embodiment of the invention, the work that is supported in catalyst of the invention on carrier
Property composition only includes noble metal platinum and tungsten oxide, and is free of any other metal active composition.
The way that amorphous silicon oxide and aluminum oxide are combined with molecular sieve is additionally used in the catalyst carrier of the present invention,
Thus the activity of catalyst acid component is improved, ensures higher lytic activity and selectivity.The amorphous silicon oxide that the present invention uses
Can be obtained by any means with aluminum oxide.For example, the aqueous solution of the aqueous solution to silicon or aluminium respectively can be passed through
PH value is adjusted and obtains the sediment of silicon hydroxide and aluminium hydroxide, then the sediment is dried, be calcined with
And the operation such as optional screening and grinding.The preparation of the amorphous silicon oxide and aluminum oxide is known to those skilled in the art
's.According to an embodiment of the invention, when preparing catalyst carrier, the pore volume of used amorphous silicon oxide is
0.5-1.1ml/g, specific surface area 200-500m2/ g, the pore volume of used amorphous alumina is 0.6-0.8ml/g, than
Surface area is 280-500m2/g。
According to another implementation of the invention, used molecular sieve is that aperture is any known more than 2 nanometers
Molecular sieve, such as ZSM, USY type molecular sieve, beta molecular sieve etc..
Catalyst carrier is modified using montmorillonite in the carrier of the present invention, increases the blending of carrier and to expensive
The adsorption capacity of metal, while the anti-impact for increasing catalyst washes performance and dimensional stability.
In the carrier of the present invention the viscous of catalyst carrier making is used as using colloidal alumina and colloidal silica
Tie agent.Colloidal alumina and colloidal silica of the present invention are materials well known in the art, can be commercially direct
Purchase, and the characteristics such as solids content therein, solid particle size, pH value and viscosity arbitrarily can be adjusted as needed
Section, to cause the catalyst carrier prepared that there is required performance.It is described according to the non-limiting embodiment of the present invention
Colloidal silica is the colloid that silica dioxide granule is formed in water, and the average grain diameter of the silica dioxide granule is received for 20~40
Rice, its pH scope is 9-10, and the molecular formula of silica contained therein can be denoted as SiO2·nH2O, with the cataloid
Gross weight on the basis of count, calculate in the form of an oxide, wherein include 15-40 weight % silica, 0.2-0.4 weight %
Na2O, and the water of surplus.The viscosity (25 DEG C) of the colloidal silica is 2-2.5MPaS, and density (25 DEG C) is 1.1-1.3
Gram per centimeter3.According to another non-limiting embodiment of the present invention, the colloidal alumina is A-4 type acidic aluminum sols,
Outward appearance is the translucent liquid of colorless and odorless, and pH value is 3.5~4.5 adjustable, and its concentration is 10~15% adjustable, high concentration can
Be dissolved in the liquid sol that various concentrations are made in water, colloidal alumina have adhesivity, thixotropy, easily disperse, water-soluble invertibity,
The characteristic such as suspension, positively charged, adsorptivity, stability.Micelle microstructure is in featheriness, positively charged, nontoxic, odorless,
It is non-volatile, non-combustible, activated alumina or high purity aluminium oxide are generated after high temperature dehydration.In the art, the colloidal silica
It is applied generally to aluminum oxide in inorfil and refractory material, as binding agent, it is also possible to make catalyst carrier.
In the present invention, when the part by weight or weight of the colloidal silica or colloidal alumina is described,
Targeted object is whole colloidal silicas or colloidal alumina, rather than only considers the solid constituent in colloid.
In addition, when describing the silica alumina ratio of carrier in the present invention, targeted object is only to be derived from amorphous
SiClx, amorphous alumina, colloidal silica and colloidal alumina binder silica and aluminum oxide between mol ratio, and
Montmorillonite, the silica of molecular sieve both components introducing and aluminum oxide are not counted.And in description molecular sieve
When silica alumina ratio, targeted is only the aluminum oxide that is included in molecular sieve and the mutual ratio of silica, is not examined
Consider the silica and aluminum oxide that other components include in carrier.
In addition, montmorillonite is a kind of natural minerals product commonly used in the art, wherein including aluminum oxide, silica and oxidation
Magnesium component, also comprising a small amount of crystallization water.Its concrete composition and molecular formula are all well known in the art.In the catalyst of the present invention
In, so-called " component for being derived from montmorillonite " represents the remaining ingredient after removing moisture under the conditions of heating and calcining." the source
From the component of montmorillonite " content in the catalyst is independently of being derived from amorphous silicon oxide, amorphous alumina, colloidal silica
The silica and aluminum oxide and molecular sieve of silicon and colloidal alumina binder and individually calculate.
When the carrier of the present invention is prepared, generally use following steps：By amorphous silicon oxide, amorphous
Aluminium, montmorillonite, molecular sieve, colloidal alumina binder and colloidal silica silicon bonding mix, and as needed optionally
Various solvents, such as water are added thereto, form the slurries that solids content is 50-60 weight %.It is excellent according to one of the present invention
Embodiment is selected, a certain amount of nitric acid is also added in the slurries.Preferably, counted on the basis of the gross weight of the slurries,
The concentration that 5-20 weight % is added into the slurries is 5 weight % dust technology.
Next, the slurries are molded by forming technique well known in the art.According to one of the present invention preferably
Embodiment, to the slurries carry out kneading and compacting, then at a temperature of 60-150 DEG C, preferably 100-120 DEG C dry 0.5-
20 hours, preferably 10-12 hours, 0.5-10 hours are then calcined at a temperature of 500-800 DEG C, preferably 600-650 DEG C, preferably
3-4 hours.
Next, by dipping-baking operation by platinum and tungsten load on the carrier.In the impregnation steps,
The carrier is put among the solution comprising platinum or tungsten, realizes that expected precious metal element is born by adjusting the concentration of solution
Carrying capacity, then the carrier after dipping is dried and is calcined.According to an embodiment of the invention, it is described comprising platinum or
The solution of tungsten is the aqueous solution of the water soluble salt of platinum or tungsten respectively, such as can use the concentration of platinum nitrate ammonium as 0.01-0.05
The aqueous solution of mol/L, and the concentration of ammonium metatungstate are the aqueous solution of 0.1-0.5 mol/Ls.In the dipping-roasting behaviour
After work, before it will be reacted, in-situ activation is carried out to the composite catalyst of gained.During this in-situ activation,
Platinum in the catalyst is reduced to zeroth order, and tungsten then remains the form of sexavalence tungsten oxide.
During the hydrocarbon raw material hydrocracking operation of the present invention, addition one or more help also into hydrocarbon raw material
The acid balance problem of acid catalysis function in hydrocracking catalyst is realized in agent, ensure persistently to adjust suitable position formed carbon just from
Son, and then the yield of midbarrel is improved, the generation of a large amount of excessive fragmentation gaseous hydrocarbons when preventing hydrogenation/dehydrogenation hyperactivity.Tool
For body, to heavy hydrocarbon is hydrocracked made from fischer-tropsch reaction when auxiliary agent used be long-chain one that carbon number is 12 to 20
One or more in first alcohol or monoacid, preferably carbon number are in 12,14,16,18 alkyl monocarbon alcohol and monoacid
One or more, the moieties of the alkyl monocarbon alcohol and monoacid can be straight chain or the saturation alkane with side chain
Base.
According in the specific embodiment of the present invention, the selection for the auxiliary agent of the specific use of the embodiment of the present invention,
Term " C12 alcohol " is specially laruyl alcohol, and term " C12 acid " is specially laurate；Term " C14 alcohol " is specially cardanol, term
" C14 acid " is specially myristic acid；Term " C16 alcohol " is specially palmityl alcohol, and term " C16 acid " is specially palmitic acid；Term " C18
Alcohol " is specially stearyl alcohol, and term " C18 acid " is specially stearic acid.
Embodiment
Following examples are used for illustrating the present invention, and by product made from these embodiments with it is existing by this area
Product made from the method for technology is contrasted.Those skilled in the art can be carried out to following embodiment as the case may be
Many modifications and variation, and it should be understood that in the case of the scope without departing from claims, the present invention can use difference
Implement in the mode illustrated herein.
Experimental method used in following examples is this area conventional method unless otherwise specified.
Following raw materials used reagent sources of example can be obtained by market, and wherein the pore volume of amorphous silicon oxide is 0.9ml/
G, specific surface area 300m2/ g, the pore volume of used amorphous alumina is 0.7ml/g, specific surface area 400m2/g.Adopted
Colloidal alumina binder and colloidal silica silicon bonding are as described above.The molecular sieve that the present invention uses is beta-molecular sieve,
Zeolite with twelve-ring macroporous structure, its silica alumina ratio are SiO2/Al2O3=23.9, aperture 3.5nm.
The synthesis hydrocarbon product that F- T synthesis hydrocarbon used in the present invention is produced by Shanxi Lu Anmeiji artificial oils Co., Ltd,
It is formed within the scope of described above.F- T synthesis hydrocarbon used in whole embodiment of the invention has complete phase
Same composition.
Embodiment 1：
Weigh 13.7 grams of amorphous silicon oxides, 27.0 grams of amorphous aluminas, 11.0 grams of montmorillonites, 14.0 gram molecules sieve,
14.0 grams of colloidal alumina binders and 14.0 grams of colloidal silica silicon bondings, and a small amount of water is added as needed, will be above-mentioned
After material is well mixed, the slurries that solids content is 80 weight % are obtained, prepare the quality hundred of various raw materials used by carrier
Point ratio is：Amorphous silicon oxide：Amorphous alumina：Montmorillonite：Molecular sieve：Silica binder：Alumina binder=1:
2:0.8:1:1:1.The dust technology that 10 gram mass fractions 5% are added into the slurries is ground, kneading and compacting, by the thing of shaping
Material is put into drying box to be dried 10 hours at 120 DEG C, and it is small that dried solid then is put into roasting 3 in 600 DEG C of Muffle furnace
When, obtain carrier.It is static by the carrier impregnation after calcining in tungsten concentration is 0.13 mol/L, 100 milliliters of ammonium metatungstate solutions
Under the conditions of impregnate 3 hours, be then placed in Muffle furnace, temperature be increased to 500 degrees Celsius with 2 DEG C/min of heating rate, and
Kept for 3 hours in this temperature.It is again that the solid impregnating after calcining is molten in the platinum nitrate ammonium of 100 milliliters of mol/Ls of concentration 0.02
In liquid, impregnate 3 hours, be then placed in Muffle furnace under quiescent conditions, 500 degrees Celsius are risen to 25 DEG C/min of heating rate,
And kept for 3 hours at this temperature.In-situ activation finally is carried out to the catalyst after calcining, first in dry nitrogen stream
Dried 2 hours in 120 DEG C in (0.5L/min), nitrogen stream is then replaced with into hydrogen stream (2L/min), heating-up temperature is risen to
400 DEG C, continue heating 3 hours to catalyst, so that its reduction activation.By operations described above obtain the present invention be used for pair
F- T synthesis hydrocarbon carries out being hydrocracked catalyst used.The composition of the catalyst is characterized using ICP, with the catalysis
Counted on the basis of the gross weight of agent, wherein Metal Supported percentage composition is：3 weight % WO3With 0.4 weight % platinum.
Next, the catalyst prepared using above step carries out the hydrocracking reaction of F- T synthesis hydrocarbon.Specific steps
It is as follows：
Embodiment prepared by above step is filled into tubular reactor, F- T synthesis hydrocarbon and auxiliary agent are passed through this together
In reactor.Wherein with the gross weight meter of the F- T synthesis hydrocarbon feed of addition, the mass percent of auxiliary agent is 0.7 weight %, institute
It is that laruyl alcohol and lauric weight are 10 to state auxiliary agent:1 mixture.At the same time, hydrogen is passed through into the reactor, with
Reach required Hydrogen Vapor Pressure and hydrogen-oil ratio.
Condition in the reactor is as follows：370 DEG C, Hydrogen Vapor Pressure 7MPa of reaction temperature, F- T synthesis hydrocarbon feed
Volume space velocity is 1.0h-1, hydrogen-oil ratio 1200.
Sampled in the exit of tubular reactor, the content of wherein various components is measured by gas chromatography, according to survey
Measure conversion ratio and target product selectivity that result calculates raw material.
Specifically, the present invention measures the content of hydro carbons of the carbon number more than 23 in product stream, and by itself and raw material
In corresponding hydrocarbon content compare, so as to obtain C23+The conversion ratio of hydro carbons, its calculation formula are as follows：
%C23+Conversion ratio=
(C23+Weight % raw materials-C23+Weight % products) * 100/C23+Weight % raw materials
In addition, the present invention also calculates the selectivity of hydrocarbon product containing carbon number between 10-22, specifically basis
C10-C22Changes of contents combination feed stock conversion COMPREHENSIVE CALCULATING before and after hydrocarbon reaction and obtain.Calculation formula is as follows：
%C10-C22Selectivity=
(C10-C22Weight % products-C10-C22Weight % raw materials) * 100/ [(C23+Weight % raw materials-
C23+Weight % products)/C23+Weight % raw materials]
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 2：
In the present embodiment, repeat the preparation process described in embodiment 1 and be prepared for catalyst, and using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 1.5 weight %, and the auxiliary agent is the mixture of following each component:Bay
Alcohol:C18 alcohol:Laurate=1:1:0.1 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：370 DEG C of reaction temperature, reactive hydrogen pressure 7MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.0h-1, hydrogen-oil ratio 1200.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 3：
In the present embodiment, repeat the preparation process described in embodiment 1 and be prepared for catalyst, and using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 2.0 weight %, and the auxiliary agent is the mixture of following each component：Bay
Alcohol:C18 alcohol:Laurate=1:1:0.5 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：380 DEG C of reaction temperature, reactive hydrogen pressure 9MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.5h-1, hydrogen-oil ratio 1200.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 4：
In the present embodiment, repeat the preparation process described in embodiment 1 and be prepared for catalyst, and using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 1.5 weight %, and the auxiliary agent is the mixture of following each component：Bay
Alcohol:C18 alcohol:Laurate=1:1:0.5 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：380 DEG C of reaction temperature, reactive hydrogen pressure 10MPa, the body of F- T synthesis hydrocarbon
Product air speed 2.0h-1, hydrogen-oil ratio 1200.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 5：
In the present embodiment, repeat the preparation process described in embodiment 1 and be prepared for catalyst, and using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 1.5 weight %, and the auxiliary agent is the mixture of following each component：Bay
Alcohol:C18 alcohol:Laurate=1:1:0.5 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：370 DEG C of reaction temperature, reactive hydrogen pressure 9MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.5h-1, hydrogen-oil ratio 1000.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 6：
In the present embodiment, repeat the preparation process described in embodiment 1 and be prepared for catalyst, and using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 1.5 weight %, and the auxiliary agent is the mixture of following each component：Bay
Alcohol:C18 alcohol:Laurate=1:1:0.5 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：380 DEG C of reaction temperature, reactive hydrogen pressure 10MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.5h-1, hydrogen-oil ratio 1200.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 7：
In the present embodiment, it is essentially repeated the preparation process described in embodiment 1 and is prepared for catalyst, but distinguishes
In, the concentration of ammonium metatungstate solution is 0.18 mol/L used by dip operation, the solution of used platinum nitrate ammonium it is dense
Spend for 0.012 mol/L, the composition of final obtained catalyst is characterized using ICP, with the gross weight of the catalyst
On the basis of count, wherein Metal Supported percentage composition is：4.7 weight % WO3With 0.19 weight % platinum.Using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.The change of its actual conditions is as follows：Closed with Fischer-Tropsch
Counted on the basis of into the weight of hydrocarbon feed, the dosage of auxiliary agent is 1.2 weight %, and the auxiliary agent is the mixture of following each component：C14
Alcohol:C18 alcohol:Laurate=1:1.5:0.3 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：380 DEG C of reaction temperature, reactive hydrogen pressure 9MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.5h-1, hydrogen-oil ratio 1000.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Embodiment 8：
In the present embodiment, it is essentially repeated the preparation process described in embodiment 1 and is prepared for catalyst, but distinguishes
In, the concentration of ammonium metatungstate solution is 0.07 mol/L used by dip operation, the solution of used platinum nitrate ammonium it is dense
Spend for 0.04 mol/L, the composition of final obtained catalyst is characterized using ICP, with the gross weight of the catalyst
On the basis of count, wherein Metal Supported percentage composition is：1.3 weight % WO3With 0.72 weight % platinum.Using the catalyst according to
Step similar to Example 1 carries out the hydrocracking reaction of F- T synthesis hydrocarbon.
The change of its actual conditions is as follows：Counted on the basis of the weight of F- T synthesis hydrocarbon feed, the dosage of auxiliary agent is 1.0 weights
% is measured, the auxiliary agent is the mixture of following each component：Laruyl alcohol:C18 alcohol:Laurate=1:1:0.5 (weight ratio).
The hydrocracking condition of F- T synthesis hydrocarbon is：380 DEG C of reaction temperature, reactive hydrogen pressure 10MPa, the body of F- T synthesis hydrocarbon
Product air speed 1.5h-1, hydrogen-oil ratio 1200.
Feed stock conversion and midbarrel are selectively shown in Table 1.
Feed stock conversion and midbarrel selective meter 1
From upper table 1, it can be seen that, by using the catalyst of the present invention, the hydrogenation carried out under conditions of it auxiliary agent be present is split
Solution reaction can realize gratifying conversion ratio and selectivity, and can significantly limit the generation of low carbon number accessory substance, by
This can be greatly enhanced the hydrocarbon hydrocracking reaction efficiency of fischer-tropsch reaction product, realize significant process improving.
Claims (21)
1. a kind of method being hydrocracked to hydro carbons, this method include：
Under conditions of it loaded catalyst and auxiliary agent be present, hydrocarbon raw material is hydrocracked；
The hydrocarbon raw material is product made from F- T synthesis, and saturation or unsaturation, the C of straight or branched are selected from comprising a variety of1-
C70The hydro carbons of hydrocarbon, and the oxidation product of optional hydrocarbon；
Counted on the basis of the weight of the loaded catalyst, platinum of the loaded catalyst comprising 0.01-3 weight %,
0.01-5 weight % tungstic acid, and the carrier of surplus, the carrier are the carriers of the oxide comprising silicon and aluminium；
The auxiliary agent is one or more straight or brancheds, saturation or undersaturated C12-C20Aliphatic monobasic alcohol and/or aliphatic
Monoacid.
2. the method as described in claim 1, it is characterised in that
The hydrocarbon raw material is product made from F- T synthesis, and saturation or unsaturation, the C of straight or branched are selected from comprising a variety of4-
C70The hydro carbons of hydrocarbon, and the oxidation product of optional hydrocarbon；Counted on the basis of the weight of the hydrocarbon raw material, the content of the auxiliary agent
For 0.5-3 weight %；
The auxiliary agent is selected from following one or more：Straight or branched, saturation or undersaturated C12 aliphatic monobasic alcohols, directly
Chain or side chain, saturation or undersaturated C14 aliphatic monobasic alcohols, straight or branched, saturation or undersaturated C16 aliphatic unitary
Alcohol, straight or branched, saturation or undersaturated C18 aliphatic monobasic alcohols, straight or branched, saturation or undersaturated C12 fat
Race's monoacid, straight or branched, saturation or undersaturated C14 Aliphatic monoacids, straight or branched, saturation or undersaturated
C16 Aliphatic monoacids, straight or branched, saturation or undersaturated C18 Aliphatic monoacids.
3. method as claimed in claim 2, it is characterised in that the auxiliary agent is selected from following one or more：Laruyl alcohol, the moon
Cinnamic acid, cardanol, myristic acid, palmityl alcohol, palmitic acid, stearyl alcohol, stearic acid.
4. the method as described in claim 1, it is characterised in that being hydrocracked for the hydrocarbon raw material is entered in the following manner
OK：The loaded catalyst is placed in reaction vessel, the mixture of hydrocarbon raw material and auxiliary agent is introduced to institute in a gaseous form
State in reactor, while introduce hydrogen into the reactor, so that hydrocracking reaction occurs for the hydrocarbon raw material；
The reaction condition of the reaction is as follows：Temperature in reaction vessel is 360-380 DEG C；The volume space velocity of the hydrocarbon raw material is
0.5-1.0h-1；Hydrogen Vapor Pressure in the reaction vessel is maintained at 5-8MPa；Using the weight of the hydrocarbon raw material as 100 weights
% meters are measured, the dosage of auxiliary agent is 0.8-3 weight %；Input the volume of the hydrogen of the reaction vessel and hydrocarbon raw material used
The ratio between normal temperature volume, i.e. hydrogen-oil ratio are 1000-1500.
5. method as claimed in claim 4, it is characterised in that counted by 100 weight % of the weight of the hydrocarbon raw material, auxiliary agent
Dosage be 1.0-2.0 weight %.
6. the method as described in claim 1, it is characterised in that counted on the basis of the weight of the loaded catalyst, it is described
The content of platinum is 0.1-0.8 weight % in loaded catalyst；The content of tungstic acid is 0.1-4.5 weight %；Surplus is load
Body.
7. the method as described in claim 1, it is characterised in that counted on the basis of the weight of the loaded catalyst, it is described
The content of platinum is 0.2-0.4 weight % in loaded catalyst；The content 2-3 weight % of tungstic acid；Surplus is carrier.
8. the method as described in claim 1, it is characterised in that the silica alumina ratio in the carrier is SiO2:Al2O3=0.1-10；
The carrier also optionally includes component and molecular sieve from montmorillonite, is counted on the basis of the gross weight of the carrier, described
The content of component from montmorillonite is 5-30 weight %, and the content of the molecular sieve is 5-20 weight %.
9. the method as described in claim 1, it is characterised in that the silica alumina ratio in the carrier is SiO2:Al2O3=0.5-5.
10. the method as described in claim 1, it is characterised in that the silica alumina ratio in the carrier is SiO2:Al2O3=0.8-
3.2。
11. the method as described in claim 1, it is characterised in that the silica alumina ratio in the carrier is SiO2:Al2O3=1.2-
2.0。
12. the method as described in claim 1, it is characterised in that the silica alumina ratio in the carrier is SiO2:Al2O3=1.5-
1.7。
13. the method as described in claim 1, it is characterised in that the loaded catalyst is prepared by following steps：
I) preparation process of carrier：By amorphous silicon oxide, amorphous alumina, colloidal alumina binder and colloidal silica
Binding agent and optional montmorillonite and molecular sieve mix, and are molded, calcining, so as to prepare carrier；
Ii) tungsten load step：The carrier is impregnated with the solution comprising tungsten, obtains required tungsten load amount, Ran Houjin
Row calcining；
Iii) platinum load step：The carrier is impregnated with the solution comprising platinum, obtains required platinum load capacity, Ran Houjin
Row calcining；
Iv) in-situ activation step：The carrier for having loaded tungsten and platinum is heated in a hydrogen atmosphere；
Wherein described step ii) and step iii) order include situations below：Step ii is carried out first), then carry out step
iii)；Or step iii is carried out first), then carry out step ii)；Or step ii) and step iii) carry out simultaneously.
14. method as claimed in claim 13, it is characterised in that for the preparation process of i) carrier, amorphous silicon oxide, nothing
Setting aluminum oxide, montmorillonite, molecular sieve, the weight ratio of colloidal alumina binder and colloidal silica silicon bonding are：
Amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina binder:Colloidal silica silicon bonding
=1:(0.5-3.0):(0.3-1.6):(0.6-1.5):(0.6-1.5):(0.6-1.5).
15. method as claimed in claim 13, it is characterised in that for the preparation process of i) carrier, amorphous silicon oxide, nothing
Setting aluminum oxide, montmorillonite, molecular sieve, the weight ratio of colloidal alumina binder and colloidal silica silicon bonding are：
Amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina binder:Colloidal silica silicon bonding
=1:(1.3-2.5):(0.7-1.2):(0.8-1.2):(0.8-1.2):(0.8-1.2).
16. method as claimed in claim 15, it is characterised in that for the preparation process of i) carrier, amorphous silicon oxide, nothing
Setting aluminum oxide, montmorillonite, molecular sieve, the weight ratio of colloidal alumina binder and colloidal silica silicon bonding are：
Amorphous silicon oxide:Amorphous alumina:Montmorillonite:Molecular sieve:Colloidal alumina binder:Colloidal silica silicon bonding
=1:2:0.8:1:1:1.
17. method as claimed in claim 13, it is characterised in that i) preparation process of carrier is carried out in the following manner：Will
Amorphous silicon oxide, amorphous alumina, montmorillonite, molecular sieve, colloidal alumina binder and colloidal silica silicon bonding mix
Altogether, the solid slurry that solids content is 50-80 weight % is formed, kneading and compacting is carried out to it, then at 60-150 DEG C
At a temperature of dry 0.5-20 hours, then at a temperature of 500-800 DEG C be calcined 0.5-10 hours, obtain the carrier.
18. method as claimed in claim 13, it is characterised in that i) preparation process of carrier is carried out in the following manner：Will
Amorphous silicon oxide, amorphous alumina, montmorillonite, molecular sieve, colloidal alumina binder and colloidal silica silicon bonding mix
Altogether, the solid slurry that solids content is 50-80 weight % is formed, kneading and compacting is carried out to it, then at 100-120 DEG C
At a temperature of dry 10-12 hours, then at a temperature of 600-650 DEG C be calcined 3-4 hours, obtain the carrier.
19. method as claimed in claim 13, it is characterised in that
Ii) tungsten load step is carried out in the following manner：Carrier is put into dipping 6-10 hours in the aqueous solution of tungstenic, it is described to contain
The concentration of tungsten is 0.1-0.5 mol/Ls in the aqueous solution of tungsten, then forges the solid after dipping at a temperature of 450-600 DEG C
Burn 1-5 hours；
Iii) platinum load step is carried out in the following manner：Will be by step ii) carrier that is handled is in the aqueous solution of platinum
6-10 hours are impregnated, the concentration of platinum is 0.01-0.05 mol/Ls in the aqueous solution of the platiniferous, then by the solid after dipping
1-5 hours are calcined at a temperature of 450-600 DEG C；
Iv) the in-situ activation step is carried out in the following manner：By step iii) obtained product in a nitrogen atmosphere,
0.5-4 hours are dried at a temperature of 100-150 DEG C, then in a hydrogen atmosphere, it is small that 2-5 are heated at a temperature of 300-500 DEG C
When, obtain the loaded catalyst.
20. method as claimed in claim 13, it is characterised in that
Ii) tungsten load step is carried out in the following manner：Carrier is put into dipping 6-10 hours in the aqueous solution of tungstenic, it is described to contain
The concentration of tungsten is 0.1-0.5 mol/Ls in the aqueous solution of tungsten, then forges the solid after dipping at a temperature of 480-550 DEG C
Burn 2-4 hours；
Iii) platinum load step is carried out in the following manner：Will be by step ii) carrier that is handled is in the aqueous solution of platinum
6-10 hours are impregnated, the concentration of platinum is 0.01-0.05 mol/Ls in the aqueous solution of the platiniferous, then by the solid after dipping
2-4 hours are calcined at a temperature of 480-550 DEG C；
Iv) the in-situ activation step is carried out in the following manner：By step iii) obtained product in a nitrogen atmosphere,
2-2.5 hours are dried at a temperature of 120-140 DEG C, then in a hydrogen atmosphere, it is small that 2-5 are heated at a temperature of 350-450 DEG C
When, obtain the loaded catalyst.
21. method as claimed in claim 13, it is characterised in that
Ii) tungsten load step is carried out in the following manner：Carrier is put into dipping 6-10 hours in the aqueous solution of tungstenic, it is described to contain
The concentration of tungsten is 0.1-0.5 mol/Ls in the aqueous solution of tungsten, then forges the solid after dipping at a temperature of 500-520 DEG C
Burn 3-3.5 hours；
Iii) platinum load step is carried out in the following manner：Will be by step ii) carrier that is handled is in the aqueous solution of platinum
6-10 hours are impregnated, the concentration of platinum is 0.01-0.05 mol/Ls in the aqueous solution of the platiniferous, then by the solid after dipping
3-3.5 hours are calcined at a temperature of 500-520 DEG C；
Iv) the in-situ activation step is carried out in the following manner：By step iii) obtained product in a nitrogen atmosphere,
2-2.5 hours are dried at a temperature of 120-140 DEG C, then in a hydrogen atmosphere, it is small that 2-5 are heated at a temperature of 400-420 DEG C
When, obtain the loaded catalyst.
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Effective date of registration: 20221216 Address after: 201,400 Building 8, No. 88, Shungong Road, Fengxian District, Shanghai Patentee after: Shanghai Xiangwei Environmental Technology Group Co.,Ltd. Address before: Room 502, 9B5, No. 100, Haike Road, Pudong New Area, Shanghai, 201210 Patentee before: SHANGHAI NACO LUBRICATION CO.,LTD. |