CN104148064B - The preparation method of the load type bimetal catalyst of a kind of activated centre high dispersive - Google Patents
The preparation method of the load type bimetal catalyst of a kind of activated centre high dispersive Download PDFInfo
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Abstract
A preparation method for the load type bimetal catalyst of activated centre high dispersive, belongs to the technical field that loaded catalyst active sites controls.Catalyst be by activated centre load on the alundum (Al2O3) of hydrotalcite in-situ modification, utilize the characteristic that hydrotalcite laminate metal cation is adjustable, trivalent promoter metal introduced hydrotalcite laminate.Hydrotalcite laminate in the process of roasting reduction, topology changes layered bi-metal oxide into, due to the lattice confinement effect of talcum laminate, controls to embed the growth of promoter metal in the process of roasting reduction in hydrotalcite laminate.And by hydrotalcite laminate to the lattice inducing action of the metal active centres platinum on laminate, realize the control to metal active centres dispersity.
Description
Technical field
The invention belongs to the technical field of control load type catalyst active center structure, in particular, provide a kind of loaded catalyst metal center and the homodisperse control method of promoter metal.
Background technology
In the process of modern social development, oil becomes one of most important energy in our life.Along with the development of society, the demand of people to the energy is increasing, and reserves is declining year by year, and " efficiency utilization of petroleum resources " just become the problem of the most critical that the whole mankind faces.Gasoline, as the important oil product of one, accounts for very important position more and more especially in the modern life.Protection for environment also becomes another key issue that in social development process, the whole mankind is concerned about; along with more and more higher to environmental requirement; more and more higher requirement be it is also proposed to vapour oil composition, namely reduce aromatic hydrocarbons, olefin(e) centent in gasoline, improve branched paraffin content and improve.
The reactions such as hydrogenolysis, cracking, isomerization, aromatisation can be there is in naphtha reforming process, carbon distribution also likely occurs, sintering causes catalysqt deactivation.Want the high octane gasoline component obtaining low arene content in naphtha reforming process.People need a kind of such catalyst, and namely low hydrogenolysis, cracking, aromatisation are selective, high isomerisation selectivity, and good stability.Namely need to reduce many Pt activated centre content that hydrogenolysis occurs, reduce the highly acid position that cracking reaction occurs.Isomerization and aromatization are all the present metal active centres dehydrogenations of direct-connected alkane, form unsaturated aliphatic hydrocarbon, then at acidic site generation cytoskeleton rearrangement, and heart hydrogenation in a metal more subsequently.
Start people from 1949 and use metal-acid bifunctional catalyst Pt/Al
2o
3-Cl completes this reaction.In order to pursue the longer operating time, nineteen sixty-eight people have developed again Pt-Re/Al
2o
3catalyst, and the carbon deposition rate successfully reducing operating pressure and catalyst, but due to the hydrogenolysis activity of Re too high, catalyst needs presulfurization before use.Hydrogenolysis needs to complete on many Pt activated centre, and in the process of presulfurization, Re defines the-Pt-ReS-Pt-species of non-activity.In order to pursue higher selective and stability, people continue again other bimetallic catalysts (Ga, Sn, In etc.) developed.Work the adding mainly by promoter metal of forefathers, affect active sites both ways, i.e. geometry and electronic mechanism.In promoter metal, a part may cover the surface of Pt, interrupts the adjacent atom of Pt, reduces many Pt activated centre content, thus it is selective to reduce hydrogenolysis; Some and Pt form alloy again, change the electronic structure of Pt thus realize lifting to catalyst effect; Some promoter metal last and carrier interact and form the oxide of more difficult reduction, and then affect activated centre electronic mechanism, improve catalytic effect, and improve stability.
Forefathers are in the design of reforming catalyst, and substantially based on making used additives change activated centre dispersity, namely promoter metal covers surface, activated centre and interrupts continuously arranged Pt atom, reduces the content in many Pt activated centre.But Pt capped when doing so just can not participate in reaction, the activated centre amount effectively that result in reduces.At present, in raising metal active centres decentralization, do large quantifier elimination, mainly contained following several approach: (1) uses chemical vapour deposition technique, but this method operating difficulties, especially not easily realize in industrial processes.(2) ion-exchange, is exchanged by exchangeable ion homodisperse on carrier and activated centre ion, then by being burnt the catalyst reducing and obtain activated centre high degree of dispersion.(3) sol-gal process, is wrapped in metal active centres in the micella of surfactant formation, is made the catalyst active center's high degree of dispersion obtained through roasting reduction by the restriction of micella.(4) coprecipitation, is synthesized activated centre in the carrier by the method for co-precipitation, because carrier is to the restriction in activated centre in the process of roasting reduction, realizes the high dispersive in activated centre.(5) optimize dipping method, comprise and control synthesis condition (immersion condition, crystallization time, reducing condition), additional supplementary mode (ultrasonic, microwave) and control slaine to drink kind of carrier.
So we design so a kind of catalyst now, the dispersity in activated centre can be controlled by the interaction controlled between carrier and activated centre.By at γ-Al
2o
3finishing hydrotalcite, promoter metal is incorporated into hydrotalcite laminate simultaneously, realize the dispersion by the net trap effect control promoter metal of hydrotalcite laminate, and control the dispersity of external source activated centre Pt by the lattice confinement of hydrotalcite laminate, realize better catalytic effect.
Hydrotalcite-based compound comprises hydrotalcite material and hydrotalcite-like materials, because its main body is generally made up of the hydroxide of two kinds of metals, therefore be otherwise known as layered di-hydroxyl composite metal oxidate (LayeredDoubleHydroxide is abbreviated as LDH).Because LDH interlayer all contains anion, therefore the intercalation compound of LDH is otherwise known as intercalated houghite.Hydrotalcite, houghite and intercalated houghite are referred to as hydrotalcite intercalation material (LDHs)
In recent years, hydrotalcite is widely applied to catalytic field with the design feature of its uniqueness, and we utilize and enter Divalent metal hydroxide to the high-valency metal confinement effect entering its lattice, limit the dispersion of high-valency metal in the process of roasting reduction.And pass through the dispersion in the lattice Induction Control external source activated centre of hydrotalcite laminate.
Summary of the invention
The object of the invention is the preparation method providing a kind of control load type bimetallic catalyst activated centre high degree of dispersion and promoter metal high degree of dispersion, realizes the control to metal active centres decentralization.
Catalyst in the present invention, for comprising PtM bimetallic catalyst, adopts the alundum (Al2O3) of hydrotalcite in-situ modification as carrier.Utilize the characteristic that hydrotalcite laminate metal cation is adjustable, promoter metal is introduced hydrotalcite laminate.Hydrotalcite laminate in the process of roasting reduction, topology changes layered bi-metal oxide into, due to the lattice confinement effect of talcum laminate, controls to embed the growth of promoter metal in the process of roasting reduction in hydrotalcite laminate.And by hydrotalcite laminate to the lattice inducing action of the metal active centres platinum on laminate, realize the control to metal active centres dispersity.
Hydrotalcite precursor of the present invention is [M
1-x 2+m
x b+(OH)
2] A
nmH
2o, wherein, M
2+be divalent metal, be preferably Mg
2+, Zn
2+, Ni
2+, Mn
2+, Cu
2+, Co
2+, Cd
2+, Ca
2+, Li
2+, Fe
2+, Pt
2+, Pd
2+deng in one or more, M
b+be high valent cationic (trivalent, tetravalent metal cation), generally all contain Al
3+, M simultaneously
b+can also comprise trivalent or and tetravalent metal cation in one or more, the preferred In of trivalent metal
3+, Fe
3+, Ga
3+, Cr
3+, Cr
3+, Co
3+, V
3+, Rh
3+, Ir
3+, Ru
3+, Sc
3+, La
3+, Mn
3+deng, the preferred Sn of tetravalent metal
4+, Zr
4+, Ti
4+deng.M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤x≤0.33.Subscript x refers to metallic element M
b+relative amount change, preferably: 0.2≤x≤0.33, A
nrepresent the tradable anion of interlayer, for electronic equilibrium.Hydrotalcite laminate has shepardite Mg (OH)
2type regular octahedron structure, cationic divalent moiety can be regarded in class shepardite laminate as by high-valence cationic same order elements, thus formation bivalent cation and high-valence cationic are positioned at the octahedra hydroxide of compound at center, these octahedrons are by limit. while share OH group covalency to be connected to form layer, layer superposes pushing up with interlayer, and interlayer associates with hydrogen bond network.Wherein M
b+be dispersed in hydrotalcite laminate with atom level.
The preparation method of the reforming catalyst in the present invention is as follows:
(1) alundum (Al2O3) modified by hydrotalcite
Divalent metal salt, high valent cationic, promoter metal salt and precipitating reagent (preferred ammoniacal liquor, urea or six tetramethyl tetramines etc.) are dissolved in deionized water, form solution A; By Al
2o
3particle immerses in solution A, transfers in autoclave, in 80 ?160 DEG C of crystallization 2 ?24h; Wherein the mol ratio of divalent metal salt, high valent cationic, promoter metal, precipitating reagent and alundum (Al2O3) is (50 ?150): (0 ?150): (1 ?100): (500 ?1500): (500 ?1500).By reaction solution suction filtration after reaction terminates, wash to eluent in neutral, the alundum (Al2O3) that the hydrotalcite obtained is modified in 80 ?160 DEG C of dryings 2 ?24h.The Al of high valent cationic
3+ be Al
2o
3stripping;
Promoter metal ion is preferably Ga
3+, In
3+, Fe
3+, Cr
3+, Sn
4+, Zr
4+, Ti
4+deng.
(2) Kaolinite Preparation of Catalyst precursor
The complex of platinum salt or platinum is dissolved in a certain amount of deionized water or in other solvents, form solution B, the alundum (Al2O3) modified the hydrotalcite that obtains in step (1) immerses in solution B, leave standstill 2 ?24h, subsequently in 80 ?160 DEG C of dryings 2 ?24h.The mol ratio of alundum (Al2O3) that wherein complex of platinum salt or platinum and hydrotalcite are modified is (1 ?10): (100 ?1000).
(3) preparation of catalyst
Catalyst precarsor prepared by step (2) in air atmosphere with 1 ?the heating rate of 20 DEG C/min rise to 300 ?1000 DEG C, roasting 2 ?24h, wherein flow velocity 10 ?100mlmin
?1g
cal ?1, subsequently with 300 ?at 1000 DEG C at H
2reduce in atmosphere 2 ?24h, wherein flow velocity be 10 ?100mlmin
?1g
cal ?1.
(4) evaluating catalyst
Catalyst application step (3) obtained is in the reaction of being reformed by normal heptane.Reaction condition be 300 ?600 DEG C, H
2flow velocity be 20 ?200mlmin
?1g
cal ?1, the flow velocity of normal heptane be 20 ?200mlmin
?1g
cal ?1.
Remarkable advantage of the present invention is that promoter metal enters between hydrotalcite laminate in preparation process, be limited in the lattice of hydrotalcite laminate, achieve uniform dispersion, but activated centre platinum does not enter laminate is subject to the lattice induction of hydrotalcite laminate, achieves the dispersion of height.High stereoselectivity can be obtained in naphtha reforming reaction, and reduce that aromatisation is selective and crackate is selective.And, catalyst in the present invention is that (hydrotalcite structure load is on alundum (Al2O3) surface for multilevel hierarchy catalyst, after calcining reduction PtM bimetallic and hydrotalcite calcined oxide thing also uniform load alundum (Al2O3) surface), be easier to commercial Application.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Zinc sulfate, gallium nitrate, six tetramethyl tetramines are dissolved in deionized water, form solution A.Alundum (Al2O3) is immersed in solution A, transfer in autoclave, with 130 DEG C of crystallization 6h.Wherein the mol ratio of zinc sulfate, gallium nitrate, six tetramethyl tetramines and alundum (Al2O3) is 150:8:800.By reaction solution suction filtration after reaction terminates, wash to eluent in neutral, the alundum (Al2O3) modified by the hydrotalcite obtained is in 80 DEG C of dry 12h.The high-valency metal that hydrotalcite laminate needs is supplemented by alundum (Al2O3) aluminium of stripping in course of reaction.
Step B: acetylacetone,2,4-pentanedione platinum is dissolved in a certain amount of deionized water or in other solvents, forms solution B, immerses in solution B, leave standstill 12h, subsequently in 80 DEG C of dry 12h by the alundum (Al2O3) that the hydrotalcite obtained in step (1) is modified.The mol ratio of alundum (Al2O3) that wherein acetylacetone,2,4-pentanedione platinum and hydrotalcite are modified is 2:1000.
Step C:
Catalyst precarsor prepared by step (2) is risen to 550 DEG C with the heating rate of 5 DEG C/min in air atmosphere, roasting 4h, wherein flow velocity 24mlmin
?1g
cal ?1, subsequently with 500 DEG C at H
2reduce 4h in atmosphere, wherein flow velocity is 18mlmin
?1g
cal ?1.
Namely prepare Pt/ZnAlGa ?LDO/Al
2o
3catalyst.
Embodiment 2
Nickel nitrate, indium nitrate, ammoniacal liquor are dissolved in deionized water, form solution A.Alundum (Al2O3) is immersed in solution A, transfer in autoclave, with 160 DEG C of crystallization 2h.Wherein the mol ratio of nickel nitrate, indium nitrate, six tetramethyl tetramines and alundum (Al2O3) is 50:5:50:1500.By reaction solution suction filtration after reaction terminates, wash to eluent in neutral, the alundum (Al2O3) modified by the hydrotalcite obtained is in 80 DEG C of dry 12h.The high-valency metal that hydrotalcite laminate needs is supplemented by alundum (Al2O3) aluminium of stripping in course of reaction.
Step B: platinic sodium chloride is dissolved in a certain amount of deionized water or in other solvents, forms solution B, immerses in solution B, leave standstill 12h, subsequently in 80 DEG C of dry 12h by the alundum (Al2O3) that the hydrotalcite obtained in step (1) is modified.The mol ratio of alundum (Al2O3) that wherein platinic sodium chloride and hydrotalcite are modified is 2:1000.
Step C:
Catalyst precarsor prepared by step (2) is risen to 550 DEG C with the heating rate of 5 DEG C/min in air atmosphere, roasting 4h, wherein flow velocity 24mlmin
?1g
cal ?1, subsequently with 500 DEG C at H
2reduce 4h in atmosphere, wherein flow velocity is 18mlmin
?1g
cal ?1.
Namely prepare Pt/NiAlIn ?LDO/Al
2o
3catalyst.
Embodiment 3
Steps A: by magnesium nitrate and urea
Magnesium nitrate, gallium nitrate, urea are dissolved in deionized water, form solution A.Alundum (Al2O3) is immersed in solution A, transfer in autoclave, with 80 DEG C of crystallization 12h.Wherein the mol ratio of magnesium nitrate, gallium nitrate, urea and alundum (Al2O3) is 30:1:200:100.By reaction solution suction filtration after reaction terminates, wash to eluent in neutral, the alundum (Al2O3) modified by the hydrotalcite obtained is in 80 DEG C of dry 12h.The high-valency metal that hydrotalcite laminate needs is supplemented by alundum (Al2O3) aluminium of stripping in course of reaction.
Step B: six amino platinum nitrates are dissolved in a certain amount of deionized water or in other solvents, form solution B, by the Al that the hydrotalcite obtained in step (1) is modified
2o
3immerse in solution B, leave standstill 12h, subsequently in 80 DEG C of dry 12h.Wherein the mol ratio of the alundum (Al2O3) of six amino platinum nitrates, gallium nitrate and hydrotalcite modification is 3:1000.
Step C:
Catalyst precarsor prepared by step (2) is risen to 550 DEG C with the heating rate of 5 DEG C/min in air atmosphere, roasting 4h, wherein flow velocity 24mlmin
?1g
cal ?1, subsequently with 500 DEG C at H
2reduce 4h in atmosphere, wherein flow velocity is 18mlmin
?1g
cal ?1.
Namely prepare Pt/MgAlGa ?LDO/Al
2o
3catalyst.
Embodiment 4
The sample obtained in the steps A of embodiment 1,2,3 is carried out X ?ray analysis of crystal structure, can observe at 2 θ is 11.90 °, 23.82 ° and 61.24 ° of vicinity, occurs the characteristic diffraction peak of (003), (006) and (110) crystal face corresponding to hydrotalcite respectively.Prove the thing phase that there is hydrotalcite structure in sample.And from the photo of ESEM, also can observe the hydrotalcite of hexagonal flake, grow at Al uniformly
2o
3surface.So can show that the growth of hydrotalcite laminate original position is at Al
2o
3surface.
Use the decentralization in activated centre in the catalyst obtained in the step C of hydroxide titration determination embodiment 1,2,3, record the activated centre decentralization in catalyst, and by calculating average grain diameter.As shown in the table
Embodiment 5
Catalyst application step (C) obtained is in the reaction of being reformed by normal heptane.Reaction condition is 500 DEG C, H
2flow velocity is 48mlmin
?1g
cal ?1, the flow velocity of normal heptane is 50mlmin
?1g
cal ?1.
Selective as shown in the table after reaching balance.
Claims (6)
1. the method for a control load type metallic catalyst activated centre high degree of dispersion, it is characterized in that, for the bimetallic catalyst of platinum and promoter metal, adopt the alundum (Al2O3) of hydrotalcite in-situ modification as carrier, utilize the characteristic that hydrotalcite laminate metal cation is adjustable, promoter metal is introduced hydrotalcite laminate, hydrotalcite laminate topology in the process of roasting reduction changes layered bi-metal oxide into, control to embed the growth of promoter metal in the process of roasting reduction in hydrotalcite laminate, and by hydrotalcite laminate to the lattice inducing action of the metal active centres platinum on laminate, realize the control to metal active centres dispersity,
Comprise the following steps:
(1) alundum (Al2O3) modified by hydrotalcite
Divalent metal salt, high valent cationic, promoter metal salt and precipitating reagent are dissolved in deionized water, form solution A; By Al
2o
3particle immerses in solution A, transfers in autoclave, in 80-160 DEG C of crystallization 2-24h; Wherein the mol ratio of divalent metal salt, high valent cationic, promoter metal salt, precipitating reagent and alundum (Al2O3) is (50-150): (0-150): (1-100): (500-1500): (500-1500); By reaction solution suction filtration after reaction terminates, wash to eluent in neutral, the alundum (Al2O3) modified by the hydrotalcite obtained is in 80-160 DEG C of dry 2-24h;
(2) Kaolinite Preparation of Catalyst precursor
The complex of platinum salt or platinum is dissolved in deionized water or in other solvents, forms solution B, the alundum (Al2O3) that the hydrotalcite obtained is modified is immersed in solution B, leave standstill 2-24h, subsequently in 80-160 DEG C of dry 2-24h in step (1); The mol ratio of alundum (Al2O3) that wherein complex of platinum salt or platinum and hydrotalcite are modified is (1-10): (100-1000);
(3) preparation of catalyst
Catalyst precarsor prepared by step (2) is risen to 300-1000 DEG C with the heating rate of 2-20 DEG C/min in air atmosphere, roasting 2-24h, wherein air velocity 10-100mlmin
-1g
cal -1, subsequently at 300-1000 DEG C at H
2reductase 12-24h, wherein H in atmosphere
2flow velocity is 10-100mlmin
-1g
cal -1.
2. according to the method for claim 1, it is characterized in that, hydrotalcite precursor [M
1-x 2+m
x b+(OH)
2] A
nmH
2o, wherein, M
2+being divalent metal, is Mg
2+, Zn
2+, Ni
2+, Mn
2+, Cu
2+, Co
2+, Cd
2+, Ca
2+, Fe
2+, Pt
2+, Pd
2+in one or more, M
b+be high valent cationic, all contain Al
3+, or M
b+also comprise trivalent or and tetravalent metal cation in one or more; M represents the quantity of the crystallization water, 0.1≤m≤0.8; Subscript x refers to metallic element M
b+relative amount change, 0.2≤x≤0.33, A
nrepresent the tradable anion of interlayer.
3. according to the method for claim 2, it is characterized in that, precipitating reagent is preferably ammoniacal liquor, urea or six tetramethyl tetramines, and promoter metal ion is preferably Ga
3+, In
3+, Fe
3+, Cr
3+, Sn
4+, Zr
4+, Ti
4+.
4. according to the method for claim 3, it is characterized in that, trivalent metal is selected from In
3+, Fe
3+, Ga
3+, Cr
3+, Co
3+, V
3+, Rh
3+, Ir
3+, Ru
3+, Sc
3+, La
3+, Mn
3+, tetravalent metal is selected from Sn
4+, Zr
4+, Ti
4+.
5. according to the catalyst that the either method of claim 1-4 prepares.
6. the reaction that the catalyst application prepared according to the either method of claim 1-4 is reformed in normal heptane.
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