CN106552646A - A kind of loaded catalyst and its preparation method and application and catalysis cycloalkane hydrogenolysis open-loop method - Google Patents
A kind of loaded catalyst and its preparation method and application and catalysis cycloalkane hydrogenolysis open-loop method Download PDFInfo
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Abstract
The invention discloses a kind of loaded catalyst, the catalyst includes carrier, load hydrogenation activity bimetallic component on this carrier and alkaline components, it is characterised in that the bimetallic component is with the weight of elemental metal than meeting (M2/M1)XPS/(M2/M1)XRF=2.0-20.0, wherein, (M2/M1)XPSIt is with the weight ratio of elemental metal, (M with second metal component of catalyst and the first metal component of x-ray photoelectron power spectrum sign2/M1)XRFIt is with the weight ratio of elemental metal with the second metal component and the first metal component in the catalyst of X-ray fluorescence spectra sign.First metal component of the present invention is Co and/or Ni, and second metal component is the transition metal of the 5th and/or period 6 group VIII.Present invention also offers the preparation method of above-mentioned catalyst and catalysis cycloalkane hydrogenolysis open-loop method.Compared with the catalyst of same metal content prepared by prior art, the loaded catalyst of the present invention has considerably higher catalysis cycloalkane hydrogenolysis open loop activity and selectivity.
Description
Technical field
The present invention relates to a kind of loaded catalyst and its preparation method and application and use the catalyst
Catalysis cycloalkane hydrogenolysis open-loop method.
Background technology
With the development of World Economics, diesel oil demand increasingly increases.Depend merely on straight-run diesel oil to meet
This demand, this is accomplished by calling in secondary processing diesel oil, such as catalytic cracking diesel oil and coker gas oil.And two
Contain substantial amounts of sulphur, nitrogen and aromatic hydrocarbons in secondary processing diesel oil, current sulphur and nitrogen can be urged with traditional sulfide
Agent is removed, and technological difficulties are the conversions of aromatic hydrocarbons.In diesel oil, high arene content can not only reduce oil
Quality, and the particle emission in diesel combustion waste gas can be increased.Generally positive structure or short side alkane
Cetane number highest, the Cetane number with long side chain cycloalkane and aromatic hydrocarbons is higher, and carries short-side chain
Or the Cetane number of unprotected side chain cycloalkane and aromatic hydrocarbons is minimum.Therefore aromatic hydrogenation saturation history is to improving diesel oil
Cetane number be it is limited, and ring-opening reaction be then hopeful improve diesel oil Cetane number.With relevant
The environmental legislation of clean energy resource is more and more harsher, and the de- virtue modification of diesel fuel becomes the emphasis of research.Cause
This, realizes that the high selectivity ring-opening reaction of cycloalkane is significant for diesel quality is improved.
Opening cyclic paraffins reaction can be carried out by three below mechanism：Radical reaction mechanism, positive carbon from
Handset is managed and hydrogenolysis mechanism (Journal of Catalysis, 2002,210,137-148).Comparatively speaking, gold
The hydrogenolysis mechanism of category catalysis selects ring-opening reaction to have higher activity and selectivity in cycloalkane, mainly
Because the ring internal tension of naphthene hydrocarbon molecule causes, and ring-opening reaction is easier than disconnected side chain reaction to be carried out.
WO/2002/007881 discloses a kind of catalyst and technique for opening cyclic paraffins, and open loop is anti-
Should be the iridium catalyst of composite carrier load by using aluminum oxide and acid Si-Al molecular sieve realizing
's.And, catalyst is exposed to roasting regeneration under 250 DEG C of oxygen atmospheres, and its open loop activity is not significantly inactivated.
CN200480043382.0 discloses a kind of catalyst and using the catalyst by opening cyclic paraffins
Method.The catalyst includes group VIII metal component, molecular sieve, refractory inorganic oxide and inessential
Modifier components.Molecular sieve includes MAPSO, SAPO, UZM-8 and UZM-15, VIII
Race's metal includes platinum, palladium and rhodium, and the preferred aluminum oxide of inorganic oxide.
CN200910013536.6 disclose a kind of naphthenic hydrocarbon hydro-conversion catalyst and preparation method thereof and
Using.Catalyst includes carrier and active metal Pt, and carrier is by Hydrogen Y-Beta composite molecular screens and nothing
Machine refractory oxide constitute, in catalyst carrier Hydrogen Y-Beta composite molecular screens content be 10wt%～
90wt%, in catalyst, the content of active metal Pt is 0.05%～0.6%.Catalyst is using dipping legal system
Standby, the catalyst for obtaining can be used for the various hydro-conversions containing cycloalkanes hydrocarbon feed.
CN201110102568.0 discloses a kind of arenes selectivity ring-opening reaction technique, reacts at two
Carry out in the reactor of series connection；Material carries out deep desulfuration and denitrification reaction into first reactor, passes through
H2S and NH3Separator desulfurization and nitrogen, when the S contents in material are less than 50ppm, N content is less than
After 10ppm, material carries out selective opening reaction into second reactor, and the reactor has two reactions
Bed, carries out being hydrogenated with saturation isomerismization reaction in first reaction bed, and second reaction bed is selected
Selecting property ring-opening reaction；First reactor selects metal sulfide catalyst；First bed of second reactor
Layer filling noble metal/molecular sieve-aluminium oxide catalyst.
But, the cycloalkane hydrogenolysis open loop activity and selectivity of catalyst disclosed above is still greatly improved
With the leeway improved.
The content of the invention
It is an object of the invention to provide a kind of with higher cycloalkane hydrogenolysis open loop activity and selectivity
Loaded catalyst and preparation method and application and catalysis cycloalkane hydrogenolysis open-loop method.
The invention provides a kind of loaded catalyst, the catalyst includes carrier, load on this carrier
Hydrogenation activity bimetallic component and alkaline components, it is characterised in that the bimetallic component is with metal
The weight of element meter is than meeting (M2/M1)XPS/(M2/M1)XRF=2-20, wherein, (M2/M1)XPSIt is with X
Second metal component of catalyst and the first metal component of X-ray photoelectron spectroscopy X sign is with elemental metal
Weight ratio, (M2/M1)XRFIt is the second metal component of catalyst and the characterized with X-ray fluorescence spectra
One metal component with the weight ratio of elemental metal, first metal component selected from for cobalt and/or nickel element,
Second metal component is the transition metal of the 5th and/or period 6 group VIII.
Present invention also offers a kind of preparation method of loaded catalyst, the method comprises the steps：
1) with the compound containing the first metal component and the solution impregnation of the compound of the second metal component
Carrier；
2) by step 1) carrier reduction activation after the dipping that obtains；
3) by step 2) product after reduction activation in reduction or inert atmosphere with containing the work of the second metal
The solution impregnation of the compound of property component；
4) with the solution impregnating carrier of the compound containing alkaline components；
Wherein, step 1) in the first metal active constituent compound and the change of the second metal active constituent
Compound is with the weight ratio of elemental metal as 10-600：1, the compound of the second metal active constituent is in step
It is rapid 1) and step 3) with the weight ratio of elemental metal as 0.01-0.8:1, first metal component is
Cobalt and/or nickel element, second metal component are the 5th and/or the transition of period 6 group VIII gold
Category element, also, the step 4) in step 1) before, among, afterwards, step 3) before,
Neutralization after any one period carry out.
Present invention also offers by obtained in said method loaded catalyst.
Present invention also offers above-mentioned loaded catalyst answering in catalysis cycloalkane hydrogenolysis ring-opening reaction
With.
Invention further provides a kind of cycloalkane hydrogenolysis open-loop method, the method is included in catalysis cycloalkanes
Under hydrocarbon hydrogenolysis open loop condition, the raw material containing cycloalkane, hydrogen are contacted with catalyst, wherein, it is described
Catalyst is above-mentioned loaded catalyst.
Compared with the catalyst of same metal content prepared by prior art, the bimetallic catalyst of the present invention
With considerably higher catalysis cycloalkane hydrogenolysis open loop activity, while with relatively low cleavage rate.Specifically,
With methyl cyclopentane as raw material, compare the hydrogenolysis open-loop performance of catalyst；As a result find, according to the present invention
Method prepare catalyst R1 be substantially better than co-impregnation preparation catalyst D1, methyl cyclopentane turn
Rate brings up to 63% from 45%, and the Cetane number increasing degree of diesel oil is improved to 10.8 from 8.9；With
Compare without alkali-metal catalyst D2, using the catalyst R1 of the inventive method preparation to methyl ring
The conversion ratio of pentane is close, but linear paraffin selectively brings up to 43% from 30%, and processes actual oil product
When Cetane number increasing degree also improve to 10.8 from 9.1.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is catalyst R1 obtained in the embodiment of the present invention 1 and comparative catalyst obtained in comparative example 1
The x-ray photoelectron energy spectrum diagram of the Ni 2p of D1；
Fig. 21 obtained contrast catalysis of catalyst R1 and comparative example obtained in the embodiment of the present invention 1
The x-ray photoelectron energy spectrum diagram of the Ir 4f of agent D1.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of loaded catalyst, the catalyst includes containing carrier, is supported on the carrier
On hydrogenation activity bimetallic component and alkali metal, it is characterised in that the bimetallic component with metal unit
The weight of element meter is than meeting (M2/M1)XPS/(M2/M1)XRF=2.0-20.0, preferred 2.5-10, more preferably 3-5,
Wherein, (M2/M1)XPSIt is the second metal component of catalyst and first characterized with x-ray photoelectron power spectrum
Metal component is with the weight ratio of elemental metal, (M2/M1)XPSIt is with urging that X-ray fluorescence spectra is characterized
The second metal component of agent and the first metal component are with the weight ratio of elemental metal, the first metal group
It is divided into cobalt and/or nickel element, second metal component is the mistake of the 5th and/or period 6 group VIII
Cross metallic element.
In the present invention, (M2/M1)XPSRefer to the second metal in the catalyst that x-ray photoelectron power spectrum is characterized
Component with the first metal component with the weight ratio of elemental metal, with respective metal elemental characteristic peak-to-peak area
Conversion draws.Wherein the measuring instrument of x-ray photoelectron power spectrum is Thermo Scientific companies
ESCALab250 type instruments, measuring condition is：Monochromator Al K α X of the excitation source for 150kW
Ray, combination can be corrected using C 1s peaks (284.8eV).
In the present invention, (M2/M1)XRFRefer to the second metal group in the catalyst that X-ray fluorescence spectra is characterized
Divide with the first metal component with the weight ratio of elemental metal.The wherein measuring instrument of X-ray fluorescence spectra
For 3271 type instrument of Rigaku electric machine industry Co., Ltd., measuring condition is：Pressed powder pellet into
Type, rhodium target, laser voltage 50kV, laser current 50mA.
According to the catalyst that the present invention is provided, on the basis of the gross weight of catalyst, the carrier
Content is 69-94 weight %, and the content of the first metal component being supported on carrier is 5-30 weight %,
The content of the second metal component is 0.05-2 weight %, and the content of alkaline components is 0.05-2 weight %.
Preferably, on the basis of the gross weight of catalyst, it is preferable that the content of the carrier is 74-89 weight %,
The content of the first metal component being supported on carrier be 10-25 weight %, the content of the second metal component
For 0.1-1 weight %, the content of alkaline components is 0.1-1 weight %.
The loaded catalyst of the present invention is that hydrogenation activity bimetal structure is special with the difference of prior art
Levy, therefore the hydrogenation activity bimetallic component can be the various conventional hydrogenation activities in hydrogenation catalyst field
Metal.Preferably, first metal component is at least one in Co or Ni, the second metal component
For at least one in Pt, Pd, Ru, Rh, Ir.
Preferably, the alkaline components are at least one in Li, Na, K, Rb, Cs.
Preferably, the carrier is aluminum oxide, silica, titanium oxide, magnesia, zirconium oxide, oxidation
One or more in thorium, beryllium oxide, clay, molecular sieve, activated carbon, more preferably silica,
One or more in aluminum oxide, Y-Beta and silica-alumina.The carrier can also be employing
One or more in phosphorus, silicon, fluorine, boron be modified after above-mentioned carrier in one or more.On
State modified carrier to be commercially available, it would however also be possible to employ existing method is modified to be obtained.
Present invention also offers the preparation method of loaded catalyst, the method comprises the steps：
1) with the compound containing the first metal component and the solution impregnation of the compound of the second metal component
Carrier；
2) by step 1) carrier reduction activation after the dipping that obtains；
3) by step 2) product after reduction activation in reduction or inert atmosphere with containing the work of the second metal
The solution impregnation of the compound of property component；
4) with the solution impregnating carrier of the compound containing alkaline components；
Wherein, step 1) in the first metal active constituent compound and the change of the second metal active constituent
Compound is with the weight ratio of elemental metal as 10-600：1, the compound of the second metal active constituent is in step
It is rapid 1) and step 3) with the weight ratio of elemental metal as 0.01-0.8:1, first metal component is
Cobalt and/or nickel element, second metal component are the periodic table of elements the 5th and/or period 6 VIII
The transition metal of race, also, the step 4) in step 1) before, among, afterwards, step
It is rapid 3) before, neutralization after any one period carry out.
As described above, the method for the present invention also includes alkali metal is introduced in carrier, wherein alkali-metal add
It can be existing various methods to enter mode, and its introducing order is also not particularly limited, as long as finally obtaining
Alkali metal is introduced in the catalyst for obtaining.Wherein, step 1) can be in step 1 before)
The compound containing alkali metal is first used to be modified carrier before.Among can be in step 1)
Or step 3) dipping solution in include the compound of alkali metal containing element, the present invention is preferably in step
3) include the compound of alkali metal containing element in dipping solution.Can be in step 1 afterwards) after
And step 2) before and/or step 3) after impregnated with the maceration extract of the compound containing alkali metal
The carrier of the first metal component and/or the second metal component is loaded.
The compound containing alkali metal can be containing in Li, Na, K, Rb, Cs at least
In a kind of nitrate, acetate, sulfate, subcarbonate, chloride, hydroxide at least
It is a kind of.
In the present invention, " with the compound of the compound containing the first metal component and the second metal component
Solution impregnating carrier " can by following manner in one or more implementing：
1) first with the solution impregnating carrier of the compound containing the first metal component, then with containing second
The solution impregnating carrier of the compound of metal component；
2) first with the solution impregnating carrier of the compound containing the second metal component, then with containing first
The solution impregnating carrier of the compound of metal component；
3) while with solution and the change containing the second metal component of the compound containing the first metal component
The solution impregnating carrier of compound；
4) compound of the compound of the first metal component and the second metal component is configured to into a kind of dipping
Liquid, then with the maceration extract impregnated carrier.
Wherein, step 1) in the first metal active constituent compound and the change of the second metal active constituent
Compound is with the weight of elemental metal than preferably 50-200：1, the compound of the second metal active constituent
In step 1) and step 3) amount ratio be preferably 0.1-0.5:1.
The compound of first metal active constituent be nitrate with Co and/or Ni as cation,
At least one in acetate, sulfate, subcarbonate, chloride.
The compound of the compound containing the first metal active constituent and the second metal active constituent
In solution, preferably in terms of the first metal active constituent, the concentration of the compound of the first metal active constituent is
500-2000 g/l, more preferably 800-1500 g/l.
The compound of second metal active constituent can be the various soluble compounds of noble metal, excellent
At least one nitrate in electing as containing Pt, Pd, Ru, Rh, Ir, acetate, sulfate, alkali
At least one in formula carbonate, chloride.
According to the present invention, step 1) in, the presence of the second metal active constituent is used to promote step 2)
In reduction reaction carrying out and step 3) in the second metal active constituent load, therefore consumption phase
Less for total consumption of the second metal active constituent, under preferable case, step 1) in the first gold medal
The compound of the compound and the second metal active constituent of category active component is with the weight ratio of elemental metal
For 50-200：1, more preferably 100-200：1.
The present invention for step 1) dipping method be not particularly limited, can be those skilled in the art
Known various methods, for example, equi-volume impregnating, supersaturation infusion process.Specifically, step 1)
The condition of dipping includes that temperature can be 10-90 DEG C, and preferably 15-40 DEG C, the time can be little for 1-10
When, preferably 2-6 hours.
Step 2) reduction activation preferably in the gaseous mixture atmosphere of pure hydrogen atmosphere or hydrogen and inert gas,
As carried out in hydrogen and the gaseous mixture atmosphere of nitrogen and/or argon gas, the condition of the reduction activation includes temperature
For 200-500 DEG C, preferably 300-500 DEG C, more preferably 350-450 DEG C, the time is 1-12 hours,
Preferably 1-5 hours, more preferably 2-4 hours.The pressure of the reduction for normal pressure can also be able to be
Pressurization, specifically, the pressure of hydrogen can be 0.1-4MPa, preferably 0.1-2MPa.In the present invention
Pressure refer to absolute pressure.
Step 3) in the compound containing the second metal active constituent solution in the second metal active constituent
Compound concentration in terms of the second metal active constituent be preferably 0.2-100 g/l, preferred 1-50 gram/
Rise.
1) solvent for use is water to preferred steps, step 2) solvent for use is water, ethanol, propyl alcohol, second
At least one in glycol, hexane, hexamethylene.
Step 3) condition that impregnates includes that temperature can be 10-90 DEG C, preferably 15-40 DEG C, the time can
Think 0.1-10 hours, preferably 0.5-2 hours.Leaching can also be supersaturated using incipient impregnation
Stain method.
Under preferable case, the step 1) adopt incipient impregnation, maceration extract volume used to press carrier suction
Water rate is calculated, step 3) used by maceration extract volume be step 1) 0.5-10 times of maceration extract volume, it is excellent
Elect 1-3 times as.
According to the present invention, said method is preferably also included step 1) carrier after the dipping that obtains first according to
Secondary drying or further roasting, then carry out the reduction activation again.
Dry temperature can be 80-150 DEG C.
The temperature of roasting can be 220-600 DEG C, and the time can be 1-6 hours.
According to the present invention, said method is preferably also included step 2) product after reduction activation is in hydrogen
And/or inert atmosphere, be such as cooled to room temperature or step 3 in nitrogen and/or argon gas) it is temperature required after enter again
Row step 3) dipping.Complete step 3) after, can also further be passed through O2/N2Volume ratio is 0.05-1.0%
Gaseous mixture 0.5-4 hours, to be passivated metal active constituent therein, obtain directly protecting in atmosphere
The catalyst deposited.
According to the present invention, said method preferably also includes to step 3) dipping after product be dried.
In order to prevent the metal active constituent in catalyst to be oxidized, the drying is preferably under vacuum or lazy
Property gas or reducibility gas protection under carry out, preferably use step 3) gas of dipping atmosphere dries up
Mode is dried to the product that dipping is obtained.
The consumption of carrier is caused on the basis of the gross weight of catalyst, and the content of the carrier is 69-94 weights
Amount %, preferably 74-89 weight %, the content of the first metal component being supported on carrier is 5-30 weights
Amount %, preferably 10-25 weight %, the content of the second metal component is 0.05-2 weight %, preferably
0.1-1 weight %, the content of alkaline components is 0.05-2 weight %, preferably 0.1-1 weight %.Should
The composition of catalyst is calculated with inventory.
According to the present invention, the carrier can be the various carriers commonly used in hydrogenation catalyst, such as aluminum oxide,
Silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, activity
One or more in charcoal, particularly preferred aluminum oxide, silica, Y-Beta and silica-alumina are carried
At least one in body.The carrier can also be to be entered using one or more in phosphorus, silicon, fluorine, boron
One or more in the modified above-mentioned carrier of row.Above-mentioned modified carrier is commercially available,
Can obtain using existing method is modified.
Compared with the catalyst of same metal content prepared by prior art, the bimetallic component of the present invention is urged
Agent has considerably higher catalysis cycloalkane hydrogenolysis open loop activity, while with relatively low cleavage rate.Study carefully
Its reason, it may be possible to which the bimetallic component catalyst for forming special construction has appropriate cycloalkane hydrogenolysis
Open loop active sites.Therefore, the top layer atom composition of catalyst is characterized using x-ray photoelectron power spectrum, is adopted
The body phase atom composition of catalyst is characterized with X-ray fluorescence spectra, the second metal component of catalyst is found
M2In the first metal component M1Surface enrichment；And the bimetallic component is with the weight ratio of elemental metal
Meet (M2/M1)XPS/(M2/M1)XRFHave in the range of=2.0-20.0 preferred 2.5-10 more preferably 3-5 more excellent
Catalytic hydrogenolysis open-loop performance.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers application of the above-mentioned loaded catalyst in cycloalkane hydrogenolysis ring-opening reaction.
Present invention also offers a kind of be catalyzed cycloalkane hydrogenolysis ring-opening reaction method, the method is included in catalysis
Under cycloalkane hydrogenolysis open loop condition, the raw material containing cycloalkane, hydrogen are contacted with catalyst, wherein,
The catalyst is above-mentioned loaded catalyst.
The catalyst of the present invention can be used for hydrogenolysis ring-opening reaction (the preferred virtue of the various raw materials containing cycloalkane
Hydrocarbon mass content is less than 15%, and sulphur mass content is less than 30ppm), such as the described original containing cycloalkane
Expect for cycloalkane model compound, or the gasoline fraction containing cycloalkane, kerosene distillate or diesel oil distillate
Deng.
The condition of haptoreaction (i.e. hydrogenolysis ring-opening reaction) is referred to prior art to be carried out, such as temperature
For 180-450 DEG C preferably 220-400 DEG C, pressure is the preferred 2-12MPa of 1-18MPa, hydrogen to oil volume ratio
For 50-10000：1 preferred 50-5000：1, mass space velocity is 0.1-100 hours-1Preferably 0.2-80
Hour-1。
The catalytic device can be enough to make the feedstock oil under hydrogenation conditions any
With carry out in the catalytic reactor of the bimetallic component catalyst, such as fixed bed reactors, slurry
State bed reactor, moving-burden bed reactor or fluidized bed reactor.
Below example facilitates a better understanding of the present invention, but does not limit the present invention.Following embodiments
In, described percentage composition if no special instructions, is weight/mass percentage composition.In following examples,
ESCALab250 type instrument of the measuring instrument of x-ray photoelectron power spectrum for Thermo Scientific companies
Device, measuring condition is：Monochromator Al K α X-ray of the excitation source for 150kW, combination can be adopted
C 1s peaks (284.8eV) are corrected；The measuring instrument of X-ray fluorescence spectra is Rigaku electric machine industry
3271 type instrument of Co., Ltd., measuring condition is：Pressed powder pellet is molded, rhodium target, laser voltage
50kV, laser current 50mA.And be simplicity, the corresponding spectrogram of embodiment 1 and comparative example 1 is only provided,
Other embodiment and comparative example directly give result of calculation.
In following examples, catalyst composition is the hydrogenation activity on the basis of the gross weight of catalyst
The weight/mass percentage composition of metallic element and alkali metal, and the composition is calculated according to inventory.
Embodiment 1
The embodiment is used to illustrate catalyst of present invention offer and preparation method thereof.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters nickeliferous 167 g/l, iridium
2.22 g/l of nickel nitrate and the dipping solution of iridium chloride.Maceration extract is decanted into into 36 grams of SiO2-Al2O3
Carrier (prepared by the embodiment 2 according to CN201110139331.X), stirs evenly at 25 DEG C after standing 4 hours,
120 DEG C of Jing drying, in 350 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1
MPa.Be down to room temperature after reduction, and add under logical hydrogen atmosphere 48.6 milliliters containing 2.96 g/l of iridium,
The mixed aqueous solution of the iridium chloride containing 2.96 g/l of potassium and potassium chloride, stands 1 hour, then is blown with hydrogen
It is dry.Then Jing O2/N2Volume ratio is that 0.5% gaseous mixture is passivated 0.5 hour, is stored in drier standby.
The catalyst for obtaining is designated as R1, and its composition, XPS and XRF characterization results are shown in Table 1, wherein X-ray
Photoelectron spectroscopy figure is as shown in Figure 1 and Figure 2.According to the electron binding energy respective peaks face of Ni 2p and Ir 4f
Product is calculated and obtains top layer atomic ratio (M2/M1)XPS。
Comparative example 1
The comparative example is used to illustrate comparative catalyst and preparation method thereof.
The comparative catalyst D1 with the same metal components of catalyst R1 is prepared according to co-impregnation.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters nickeliferous 167 g/l, iridium
6.67 g/l, the dipping solution of the nickel nitrate, iridium chloride and potassium chloride of 4.44 g/l of potassium.By maceration extract
It is decanted into 36 grams of SiO2-Al2O3Carrier (prepared by the embodiment 2 with reference to CN201110139331.X),
Stir evenly at 25 DEG C, after standing 4 hours, 120 DEG C of drying of Jing, in 350 DEG C of roastings 4 hours, 350 DEG C of hydrogen
Gas is reduced 4 hours, and Hydrogen Vapor Pressure is 0.1 MPa.Room temperature, Jing O are down to after reduction2/N2Volume ratio is
0.5% gaseous mixture is passivated 0.5 hour, is stored in drier standby.The catalyst for obtaining is designated as D1, its
Composition, XPS and XRF characterization results are shown in Table 1.Wherein x-ray photoelectron energy spectrum diagram is as shown in Figure 1, Figure 2
It is shown.
Comparative example 2
Method according to embodiment 1 prepares catalyst, except for the difference that, in maceration extract used by second dipping
Alkali metal is not contained, comparative catalyst D2 is obtained, its composition, XPS and XRF characterization results are shown in
Table 1.
Comparative example 3
Method according to embodiment 1 prepares catalyst, except for the difference that, loads the first metal drying and roasting
Bimetallic load is directly carried out without reducing under hydrogen atmosphere afterwards, comparative catalyst D3 is obtained,
Its composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 2
The embodiment is used to illustrate catalyst of present invention offer and preparation method thereof.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters containing 167 g/l of cobalt, platinum
1.11 g/l of cobalt nitrate and the dipping solution of tetraammineplatinum chloride.Maceration extract is decanted into into 36 grams of Hydrogens
Y-Beta composite molecular screens-alumina support are (according to the carrier D1 of the embodiment 1 of CN101992120A
Prepare), stir evenly at 25 DEG C, after standing 4 hours, 110 DEG C of drying of Jing, in 500 DEG C of roastings 4 hours,
350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure are 0.1 MPa.Room temperature is down to after reduction, and in logical hydrogen
1.85 g/l of 48.6 milliliters of platiniferous, the tetraammineplatinum chloride containing 1.48 g/l of sodium and chlorine are added under atmosphere
Change the mixed aqueous solution of sodium, stand 1 hour, then dried up with hydrogen.Then Jing O2/N2Volume ratio is 0.5%
Gaseous mixture be passivated 0.5 hour, be stored in drier standby.The catalyst for obtaining is designated as R2, its composition,
XPS and XRF characterization results are shown in Table 1.
Comparative example 4
Illustrate comparative catalyst and preparation method thereof.
The method provided according to CN101992120A embodiments 1 prepares catalyst D4.
The metal salt concentration as needed for equi-volume impregnating, is configured to the two of 3.89 g/l of 32.4 milliliters of platiniferous
The dipping solution of four ammino platinum of chlorine.Maceration extract is decanted into into 41.4 grams of Hydrogen Y-Beta composite molecular screens-oxygen
Change alumina supporter, stir evenly at 25 DEG C, after standing 4 hours, 110 DEG C of drying of Jing are little in 500 DEG C of roastings 4
When, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure are 0.1 MPa.Room temperature, Jing O are down to after reduction2/N2
Volume ratio is that 0.5% gaseous mixture is passivated 0.5 hour, is stored in drier standby.The catalyst for obtaining is designated as
D4, its composition are shown in Table 1.
Embodiment 3
The embodiment is used to illustrate catalyst of present invention offer and preparation method thereof.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters nickeliferous 111 g/l, palladium
2.22 g/l of nickel nitrate and the dipping solution of palladium nitrate.Maceration extract is decanted into into 36 grams of SiO2-Al2O3
Carrier (prepared by the embodiment 2 according to CN201110139331.X), stirs evenly after standing 4 hours, Jing
120 DEG C of drying, in 350 DEG C of roastings 4 hours, 450 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure is 1,000,000
Handkerchief.Room temperature is down to after reduction, and under logical hydrogen atmosphere adds 48.6 milliliters to contain 5.19 g/l of palladium, lithium
3.70 g/l of palladium nitrate and the mixed aqueous solution of lithium nitrate, stir evenly at 15 DEG C, stand 6 and stand 1 hour,
Dried up with hydrogen again.Then Jing O2/N2Volume ratio is that 1% gaseous mixture is passivated 0.5 hour, is stored in drying
Device is standby.The catalyst for obtaining is designated as R3, and its composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 4
The embodiment is used to illustrate catalyst of present invention offer and preparation method thereof.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters nickeliferous 167 g/l, ruthenium
2.22 g/l of nickel nitrate and the dipping solution of ruthenic chloride.Maceration extract is decanted into into 36 grams of γ-Al2O3Carry
Body (Chang Ling catalyst plant product, granularity 20-40 mesh are identical once), 40 DEG C stir evenly standing 2 hours
Afterwards, 120 DEG C of Jing drying, in 550 DEG C of roastings 1 hour, 400 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure
For MPa.Be down to room temperature after reduction, and add under logical hydrogen atmosphere 48.6 milliliters containing 2.96 g/l of ruthenium,
Mixing water-ethanol solution (water and the ethanol volume ratio 1 of the ruthenic chloride containing 2.96 g/l of potassium and potassium chloride：1),
1 hour is stood, then is dried up with hydrogen.Then Jing O2/N2Volume ratio is 0.5% gaseous mixture passivation 2
Hour, it is stored in drier standby.The catalyst for obtaining is designated as R4, and its composition, XPS and XRF are characterized
The results are shown in Table 1.
Embodiment 5
The embodiment is used to illustrate catalyst of present invention offer and preparation method thereof.
The metal salt concentration as needed for equi-volume impregnating, is configured to 32.4 milliliters containing 244 g/l of cobalt, iridium
2.22 g/l, the dipping solution of the cobalt nitrate, iridium chloride and potassium nitrate of 4.44 g/l of potassium.By maceration extract
It is decanted into 36 grams of γ-Al2O3Carrier, stirred evenly standing after 4 hours, and 120 DEG C of drying of Jing are roasted at 350 DEG C
Burn 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa.Room temperature is down to after reduction,
And the water-ethanol solution (water of 48.6 milliliters of iridium chlorides containing 2.96 g/l of iridium is added under logical hydrogen atmosphere
With ethanol volume ratio 1：1) 1 hour is stood, then is dried up with hydrogen.Then Jing O2/N2Volume ratio is
0.5% gaseous mixture is passivated 0.5 hour, is stored in drier standby.The catalyst for obtaining is designated as R4, its
Composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 6-10
These embodiments are used for the catalyst for illustrating present invention offer to model compound methyl cyclopentane
Catalytic hydrogenolysis open-loop results.
Evaluate catalyst R1, R2, R3, R4 and R5 as steps described below respectively.
Activity rating is carried out to catalyst on continuous flowing fixed-bed micro-devices, feedstock oil is modelling
Compound methyl cyclopentane, loaded catalyst are 0.5 gram, and reaction condition is：Pressure is 3.0 MPas,
Feedstock oil input is 0.2 ml/min, and hydrogen to oil volume ratio is 1000, and temperature is 260 DEG C, and reaction 3 is little
When after sampling carry out online gas chromatographic analysis.Before reaction starts, first 260 DEG C, 3.0 MPas,
The nitrogen atmosphere reductase 12 hour of 200 ml/min of flow velocity.Reaction result is listed in table 2.
Comparative example 5-8
These comparative examples are used for the hydrogenolysis open loop activity for illustrating comparative catalyst.
Comparative catalyst D1-D4 is evaluated respectively according to method same as Example 6 and condition.Reaction knot
Fruit is listed in table 2.
Table 1
Table 2
| Embodiment is numbered | Catalyst is numbered | Methyl cyclopentane conversion ratio (%) | Linear paraffin is selective (%) |
| Embodiment 6 | R1 | 63 | 43 |
| Comparative example 5 | D1 | 45 | 32 |
| Comparative example 6 | D2 | 61 | 30 |
| Comparative example 7 | D3 | 44 | 35 |
| Embodiment 7 | R2 | 57 | 45 |
| Comparative example 8 | D4 | 46 | 39 |
| Embodiment 8 | R3 | 54 | 40 |
| Embodiment 9 | R4 | 56 | 40 |
| Embodiment 10 | R5 | 62 | 42 |
Embodiment 11-15
Hydrogenolysis open loop activity during the catalyst treatment oil product that these embodiments explanation present invention is provided.
Evaluate catalyst R1, R2, R3, R4 and R5 as steps described below respectively.
On 30 milliliters of hydrogenation plants, with the catalytic cracking after deep hydrodesulfurizationof aromatic moiety saturation
Diesel oil be reaction raw materials (9.5 weight % of total arene content, sulfur content 8.1ppm, Cetane number 39.2),
Carry out the open loop activity rating of oil product.20 milliliters of loaded catalyst, and 30 millis are diluted to quartz sand
Rise, granularity is all 20～40 mesh.Before reaction starts, first 290 DEG C, 6.0 MPas, flow velocity 200
The nitrogen atmosphere of ml/min is reduced 4 hours.Then, in the case where temperature, pressure are constant, by liquid
Volume space velocity 1.5 hours-1, activity rating is carried out to catalyst under conditions of hydrogen to oil volume ratio 800, is reacted
Sample after stablizing 24 hours, analysis generates the Cetane number of diesel oil.Evaluation result is shown in Table 3.
Comparative example 9-12
The comparative example is used to illustrate open loop activity during comparative catalyst's process oil product.
Comparative catalyst D1-D4 is evaluated respectively according to 11 identical method of embodiment and condition.Reaction
As a result it is listed in table 3.
3 catalyst treatment oil product evaluation result of table
| Embodiment is numbered | Catalyst is numbered | Cetane number value added |
| Embodiment 11 | R1 | 10.8 |
| Comparative example 9 | D1 | 8.9 |
| Comparative example 10 | D2 | 9.1 |
| Comparative example 11 | D3 | 8.9 |
| Embodiment 12 | R2 | 10.4 |
| Comparative example 12 | D2 | 9.1 |
| Embodiment 13 | R3 | 9.9 |
| Embodiment 14 | R4 | 10.0 |
| Embodiment 15 | R5 | 10.3 |
By embodiment 6 and comparative example 5, and the result of embodiment 11 and comparative example 9 can be seen that and adopt
The catalyst R1 prepared with the inventive method is substantially better than the catalyst D1 of co-impregnation preparation, methyl ring
The conversion ratio of pentane brings up to 63% from 45%, to the Cetane number increasing degree of diesel oil from 8.9 improve to
10.8.By embodiment 6 and comparative example 6, and the result of embodiment 11 and comparative example 10 can be seen that
Compared with without alkali-metal catalyst D2, using the catalyst R1 of the inventive method preparation to methyl
The conversion ratio of pentamethylene is close, but linear paraffin selectively brings up to 43% from 30%, and processes actual oil
During product, Cetane number increasing degree is also improved to 10.8 from 9.1.
By embodiment 7 and comparative example 8, and the result of embodiment 12 and comparative example 12 can be seen that
Single Pt catalyst D4 of composite molecular screen load is better than using catalyst R2 prepared by the inventive method,
The conversion ratio of methyl cyclopentane brings up to 57% from 46%, to the Cetane number increasing degree of diesel oil from 9.1
Improve to 10.4.
These embodiment results illustrate that catalyst provided by the present invention is identical expensive with prepared by prior art
The catalyst of tenor is compared, and with more preferable opening cyclic paraffins activity, diesel cetane-number is had
Bigger increase rate.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment,
In the case of reconcilable, can be combined by any suitable means.In order to avoid unnecessary
Repeat, the present invention is no longer separately illustrated to various possible combinations.
Claims (21)
1. a kind of loaded catalyst, the catalyst include that carrier, load hydrogenation on this carrier are lived
Property metal component and alkaline components, the hydrogenation active component include the first metal component and the second metal
Component, it is characterised in that the catalyst meets (M2/M1)XPS/(M2/M1)XRF=2-20, wherein,
(M2/M1)XPSIt is the second metal component and the first metal in the catalyst characterized with x-ray photoelectron power spectrum
Component is with the weight ratio of elemental metal, (M2/M1)XRFIt is the catalyst characterized with X-ray fluorescence spectra
, with the weight ratio of elemental metal, first metal component is for second metal component and the first metal component
Cobalt and/or nickel element, second metal component are the 5th and/or the transition of period 6 group VIII gold
Category element.
2. catalyst according to claim 1, wherein, the catalyst meets
(M2/M1)XPS/(M2/M1)XRF=2.5-10, the preferably catalyst meet (M2/M1)XPS/(M2/M1)XRF=
3-5。
3. catalyst according to claim 1 and 2, wherein, the gross weight with catalyst is as base
Standard, the content of the carrier is 69-94 weight %, the content of the first metal component being supported on carrier
For 5-30 weight %, the content of the second metal component is 0.05-2 weight %, and the content of alkaline components is
0.05-2 weight %；Preferably, the content of the carrier is 74-89 weight %, is supported on carrier
The content of the first metal component is 10-25 weight %, and the content of the second metal component is 0.1-1 weight %,
The content of alkaline components is 0.1-1 weight %.
4. the catalyst according to any one in claim 1-3, wherein, the second metal component
For at least one in Pt, Pd, Ru, Rh, Ir, alkaline components are Li, Na, K, Rb, Cs
In at least one.
5. the catalyst according to any one in claim 1-4, wherein, the carrier is oxygen
Change aluminium, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve,
One or more in activated carbon.
6. the catalyst according to any one in claim 1-5, wherein, the X-ray light
Electron spectrum adopts excitation source and measures for the monochromator Al K α X-rays of 150kW, the X-ray
It is 50kV that the measuring condition of fluorescence spectrum includes rhodium target, laser voltage and laser current is 50mA.
7. a kind of preparation method of loaded catalyst, the preparation method comprise the steps：
1) with the compound containing the first metal component and the solution impregnation of the compound of the second metal component
Carrier；
2) by step 1) carrier reduction activation after the dipping that obtains；
3) by step 2) product after reduction activation in reduction or inert atmosphere with containing the work of the second metal
The solution impregnation of the compound of property component；
4) with the solution impregnating carrier of the compound containing alkaline components；
Wherein, step 1) in the first metal active constituent compound and the change of the second metal active constituent
Compound is with the weight ratio of elemental metal as 10-600：1, the compound of the second metal active constituent is in step
It is rapid 1) and step 3) with the weight ratio of elemental metal as 0.01-0.8:1, first metal component is
Cobalt and/or nickel element, second metal component are the 5th and/or the transition of period 6 group VIII gold
Category element, also, the step 4) in step 1) before, among, afterwards, step 3) before,
Neutralization after any one period carry out.
8. preparation method according to claim 7, wherein, step 1) in the first metal active group
The compound for dividing and the compound of the second metal active constituent are with the weight ratio of elemental metal as 50-200：
1, the compound of the second metal active constituent is in step 1) and step 3) amount ratio be 0.1-0.5:1.
9. the preparation method according to claim 7 or 8, wherein, the compound of alkaline components
Be containing Li, Na, K, Rb, Cs in one or more nitrate, acetate, sulfate, alkali
At least one in formula carbonate, chloride, hydroxide.
10. the preparation method according to any one in claim 7-9, wherein, step 1) leaching
The condition of stain includes temperature for 10-90 DEG C, preferably 15-40 DEG C, and the time is 1-10 hours, preferably
2-6 hours.
11. preparation methods according to any one of claims of claim 7-10, wherein, step 2) also
Former activation is carried out in a hydrogen atmosphere, and the condition of the reduction activation includes temperature for 200-500 DEG C, when
Between be 1-12 hours.
12. preparation methods according to any one in claim 7-11, wherein, step 3) leaching
The condition of stain includes temperature for 10-90 DEG C, and the time is 0.1-10 hours.
13. preparation methods according to any one in claim 7-12, wherein, the method is also
Including by step 1) carrier after the dipping that obtains first is dried and roasting successively, then carries out institute again
State reduction activation.
14. preparation methods according to any one in claim 7-13, wherein, the method is also
Including by step 2) product after reduction activation is cooled to room temperature or step 3 under hydrogen or inert atmosphere)
Carry out step 3 after temperature required again) described in dipping.
15. preparation methods according to any one in claim 7-14, wherein, the method is also
Including to step 3) solid that obtains is passed through O2/N2Volume ratio is little for the gaseous mixture 0.5-4 of 0.05-1.0%
When, to be passivated metal active constituent therein, obtain the catalyst that directly can be preserved in atmosphere.
16. preparation methods according to any one in claim 7-15, wherein, the first metal
The consumption of component, the second metal component and alkaline components is caused on the basis of the gross weight of catalyst, institute
The content for stating carrier is 69-94 weight %, and the content of the first metal component being supported on carrier is 5-30
Weight %, the content of the second metal component is 0.05-2 weight %, and the content of alkaline components is 0.05-2
Weight %.
17. preparation methods according to any one in claim 7-16, wherein, the carrier
For aluminum oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, point
One or more in son sieve, activated carbon.
Loaded catalyst obtained in preparation method in 18. claims 7-17 described in any one.
Loaded catalyst in 19. claims 1-6 and 18 described in any one is in cycloalkane hydrogenolysis
Application in ring-opening reaction.
A kind of 20. cycloalkane hydrogenolysis open-loop methods, the method are included in catalysis cycloalkane hydrogenolysis open loop condition
Under, the raw material containing cycloalkane, hydrogen are contacted with catalyst, wherein, the catalyst will for right
Seek the loaded catalyst described in any one in 1-6 and 18.
21. cycloalkane hydrogenolysis open-loop methods according to claim 20, wherein, the catalysis ring
Alkane hydrogenolysis open loop condition includes temperature for 180-450 DEG C preferably 220-400 DEG C, and pressure is 1-18MPa
It is preferred that 2-12MPa, hydrogen to oil volume ratio is 50-10000：1 preferred 50-5000：1, mass space velocity is
0.1-100 hours-1Preferably 0.2-80 hours-1。
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