CN104148120A - Method for controlling high dispersion of metal centers for catalysts by using auxiliaries - Google Patents
Method for controlling high dispersion of metal centers for catalysts by using auxiliaries Download PDFInfo
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- CN104148120A CN104148120A CN201410277103.2A CN201410277103A CN104148120A CN 104148120 A CN104148120 A CN 104148120A CN 201410277103 A CN201410277103 A CN 201410277103A CN 104148120 A CN104148120 A CN 104148120A
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Abstract
The invention relates to a method for controlling high dispersion of metal centers for catalysts by using auxiliaries, belonging to the technical field of supported catalyst controlling. Through uniform dispersion of layered double hydrotalcite precursor layer board cations, uniform doping, namely high dispersion of auxiliary metal ions in roasting oxides is realized, an electronic structure on a carrier surface is modulated, and the anchor points of Pt metal centers are provided. The method is easy to operate and control, the types and the content of the auxiliaries can be adjusted, and a control agent is not needed, so that single-atom-dispersed or atomic cluster Pt metal centers are obtained.
Description
Technical field
The invention belongs to loaded catalyst control technology field, the control method that particularly provides a kind of catalyst metals centre-height to disperse.
Background technology
The catalytic activity of load type metal catalyst Yin Qigao and selectively in industrial extensive use.For load type metal catalyst, in general metal particle size effect is the important factor in order of catalyst performance, especially noble metal catalyst, due to the requirement of its expensive cost and reaction itself, mostly needs the activated centre of high dispersive.And a lot of situations of the control at metal active center rely on auxiliary agent.Be different from catalyst active center, auxiliary agent refers to add and in catalyst or catalyst system and catalyzing, improves rate of catalysis reaction or material optionally.If there is no catalyst, auxiliary agent itself does not have obvious catalytic activity.But auxiliary agent has played important function in the control of catalyst active center, for example catalytic reforming, a kind of important petrochemical process, by auxiliary agent tin, indiums etc. add the catalyst based decentralization that improves platinum of load type platinum, thereby improve the selective and stability of catalytic reaction.In load type metal catalyst, auxiliary agent is generally one or more metallic elements, can be metallic state or ionic state.Auxiliary agent is generally divided into electronic action and acts on two kinds how much for the control of catalyst active center.Electronic action is the cloud density that shifts modulation active metal center by the electronics between promoter metal center and active metal center, improves metal center decentralization; How much effects refer to that promoter metal is dispersed in active metal group, by spaced active metal atom to obtain the high dispersive of metal center.
At present, adding of auxiliary agent is generally conventional impregnation, or by controls such as surfactants, the decentralization of auxiliary agent is low, disperses inhomogeneously, is difficult to well and metal active central role.And controlling agent mostly is organic matter, owing to removing difficulty, residue directly affects catalyst activity.
Layered double hydroxide claims again hydrotalcite (Layered Double Hydroxide, LDH), the divalence of its laminate and Tricationic are highly dispersed on laminate, can introduce the second high-valence cationic (auxiliary agent) and replace part trivalent metal cation, the promoter metal ion doping of introducing is in divalent metal gap.Through high-temperature roasting, hydrotalcite precursor topology changes metal oxide into, realizes the lattice location to promoter metal, makes promoter metal height dispersed.By different promoter metal doping modulation carriers electron structures, provide metal cluster even monoatomic anchored site, realize for the induction load of exogenous noble metal (such as platinum) metal center, obtain the loaded noble metal catalyst of the high degree of dispersion of monatomic or monatomic rank bunch.
Summary of the invention
The object of the invention is to provide a kind of method that improves load type metal catalyst metal center decentralization, taking hydrotalcite as precursor, utilize the controlled and laminate lattice orientation effect of the laminate of LDHs, promoter metal is introduced to laminate with the cationic form of laminate, through high-temperature roasting, hydrotalcite precursor topology changes and forms metal oxide, realize the lattice grappling to promoter metal, further induce carried noble metal to realize bunch dispersion of the monatomic and monatomic rank of noble metal (such as platinum) metal center.
Hydrotalcite precursor of the present invention is [M
2+ 1-am
n+ a(OH)
2]
x+[A
y-] mH
2o, wherein, M
2+be divalent metal, be preferably Zn
2+, Mg
2+, Ni
2+, Mn
2+deng in one, M
n+trivalent metal cation and a kind of promoter metal cation, the preferred Al of trivalent metal cation
3+, promoter metal cation is that Tricationic is as In
3+, Fe
3+, Cr
3+deng, or quadrivalent cation Sn
4+, Zr
4+, Ti
4+deng replacing original Tricationic Al
3+enter the metal cation of hydrotalcite laminate, the cationic molar percentage of promoter metal is controlled in 10%, A
y-the anion that enters interlayer, preferably CO
3 2-, with the unnecessary positive charge of balance laminate.M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤a≤0.33.
The design feature of this hydrotalcite precursor is: laminate high-valence cationic is dispersed between bivalent cation, thereby realizes the cationic high dispersive of promoter metal.
In addition, this can be had to the Al of high-specific surface area by hydrotalcite containing auxiliary agent
2o
3, SiO
2or TiO
2growth in situ in the matrix such as bead, forms multilevel hierarchy, can better dispersing aid and precious metal catalyst activated centre, obtain being more suitable for the catalyst structure of commercial Application.
The control of this loaded catalyst metal high degree of dispersion, is by the laminate cation of modulation hydrotalcite precursor, realizes the high degree of dispersion of promoter metal; By the lattice location modulation carriers electron structure of auxiliary agent, further control the high degree of dispersion of Pt metal center again.Its step is as follows:
A. prepare hydrotalcite precursor [M
2+ 1-am
n+ a(OH)
2]
x+[A
y-] mH
2o, wherein, M
2+be divalent metal, be preferably Zn
2+, Mg
2+, Ni
2+, Mn
2+deng in one, M
n+be high valent cationic, select Al
3+with a kind of promoter metal cation, as In
3+, Fe
3+, Ga
3+, Cr
3+deng, or Sn
4+, Zr
4+, Ti
4+deng the metal cation that can replace Tricationic and enter hydrotalcite laminate, the molar percentage of auxiliary agent is controlled in 10%;
B. the soluble compound of noble metal (such as platinum, palladium, gold etc.) element is deposited on hydrotalcite precursor by conventional method, such as by platinum salt or containing the aqueous solution of platinum compounds or organic solution incipient impregnation to the hydrotalcite precursor making in a, washing, dry; While selecting platinum, platinum load capacity is 0.2wt%-3wt%, preferably 0.3wt%;
C. the catalyst precarsor making in b is incubated to 1-5h high-temperature roasting at tube furnace 400-850 DEG C, then uses H
2reduce, can obtain the loaded catalyst of metal center high degree of dispersion.
M in step a
n+auxiliary agent cation comprises above-mentioned In
3+, Fe
3+, Ti
4+, Sn
4+, Zr
4+deng.
In step b, mention platinum salt or have chloroplatinic acid containing platinum compounds, sodium chloroplatinate, ammoniation, ammonium chloroplatinate, and organic platinum source is as dihydroxy platinous chloride, six hydroxyl platinic acid etc.
Hydrotalcite precursor methods control promoter metal of the present invention is doped to metal oxide MO (M=Zn, Mg, Ni, Mn, Cd etc.) lattice, the lattice positioning action of laminate makes auxiliary agent high degree of dispersion, and make its electronic structure that corresponding change occur, thereby realize the induction load to Pt, obtain the Pt metal center of single atomic dispersion.Wherein auxiliary agent is one or more in In, Fe, Sn, Zr, Ge, Ti, Mo, Cr, Bi, Mn, W.
Be high degree of dispersion by promoter metal ion at the Uniform Doped of roasting oxidation thing, and modulation carrier surface electronic structure, the anchored site of the metal centers such as Pt is provided.Hydrotalcite precursor is carried out to XRD sign and show that auxiliary agent cation just can be as hydrotalcite laminate, carrier is carried out to XRD, HRTEM phenetic analysis, HRTEM has significant change containing the support crystal lattice width of fringe of auxiliary element, meet ionic radius Changing Pattern, Display Realization the lattice location of promoter metal atom.Catalyst is carried out to STEM and characterize bunch dispersion of finding the monatomic and monatomic rank that has realized platinum center.
Brief description of the drawings
Fig. 1 is the STEM figure of catalyst;
(a) atomicity of comparative example 1 platinum dispersity and platinum 2D bunch statistics; (b) atomicity of the platinum dispersity of embodiment 1 and platinum 2D bunch (monatomic rank platinum) statistics; (c) atomicity of the platinum dispersity of embodiment 2 and platinum 2D bunch (monatomic rank platinum) statistics; (d) atomicity of the platinum dispersity of embodiment 3 and platinum 2D bunch (monatomic rank platinum) statistics.
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
Steps A: by 0.01mol Mg (NO
3)
26H
2o, 0.0015mol Al (NO
3)
39H
2o, 0.001mol SnCl
46H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains MgAlSn-LDHs.
Step B: take 2g MgAlSn-LDHs (making in steps A), incipient impregnation H
2[PtCl
6] 6H
2the O aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain Pt/MgAlSn-LDHs.
Step C: by the Pt/MgAlSn-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/MgAlSn-MMO, and the sample that takes a morsel characterizes.
Comparative example 1
Steps A: by 0.01mol Mg (NO
3)
26H
2o, 0.005mol Al (NO
3)
39H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains MgAl-LDHs.
Step B: take 2g MgAl-LDHs (making in steps A), incipient impregnation SnCl
4the aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain PtSn/MgAl-LDHs.
Step C: by the PtSn/MgAl-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain PtSn/MgAl-MMO, and the sample that takes a morsel characterizes.
Embodiment 2
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.0015mol Al (NO
3)
39H
2o, 0.001mol SnCl
46H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAlSn-LDHs.
Step B: take 2g ZnAlSn-LDHs (making in steps A), incipient impregnation H
2[PtCl
6] 6H
2the O aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain Pt/ZnAlSn-LDHs.
Step C: by the Pt/ZnAlSn-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/ZnAlSn-MMO, and the sample that takes a morsel characterizes.
Comparative example 2
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.005mol Al (NO
3)
39H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAl-LDHs.
Step B: take 2g ZnAl-LDHs (making in steps A), incipient impregnation SnCl
4the aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain PtSn/ZnAl-LDHs.
Step C: by the PtSn/ZnAl-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain PtSn/ZnAl-MMO, and the sample that takes a morsel characterizes.
Embodiment 3
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.0015mol Al (NO
3)
39H
2o, 0.001mol ZrO (NO
3)
26H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAlZr-LDHs.
Step B: take 2g ZnAlZr-LDHs (making in steps A), incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 100 DEG C of dry 12h, obtain Pt/ZnAlZr-LDHs.
Step C: by the Pt/ZnAlZr-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/ZnAlZr-MMO, and the sample that takes a morsel characterizes.
Comparative example 3
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.005mol Al (NO
3)
39H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 55 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAl-LDHs.
Step B: take 2g ZnAl-LDHs (making in steps A), incipient impregnation ZrO (NO
3)
26H
2the O aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 100 DEG C of dry 12h, obtain PtZr/ZnAl-LDHs.
Step C: by the PtZr/ZnAl-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/ZrO
2-ZnAl-MMO, the sample that takes a morsel characterizes.
Embodiment 4
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.0015mol Al (NO
3)
39H
2o, 0.001mol Fe (NO
3)
39H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAlFe-LDHs.
Step B: take 2g ZnAlFe-LDHs (making in steps A), incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain Pt/ZnAlFe-LDHs.
Step C: by the Pt/ZnAlFe-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/ZnAlFe-MMO, and the sample that takes a morsel characterizes.
Comparative example 4
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 0.005mol Al (NO
3)
39H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 55 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAl-LDHs.
Step B: take 2g ZnAl-LDHs (making in steps A), incipient impregnation Fe (NO
3)
39H
2the O aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 100 DEG C of dry 12h, obtain PtFe/ZnAl-LDHs.
Step C: by the PtFe/ZnAl-LDHs obtaining 750 DEG C of insulation 300min in Muffle furnace, be down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain PtFe/ZnAl-MMO, and the sample that takes a morsel characterizes.
Embodiment 5
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 2g Al
2o
3bead, 0.001mol SnCl
46H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 55 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAlSn-LDHs/Al
2o
3.
Step B: take 2g ZnAlSn-LDHs-Al
2o
3(in steps A, making), incipient impregnation H
2[PtCl
6] 6H
2the O aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain Pt/ZnAlSn-LDHs/Al
2o
3.
Step C: by the Pt/ZnAlSn-LDHs-Al obtaining
2o
3in Muffle furnace, 750 DEG C of insulation 300min, are down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pt/ZnAlSn-MMO/Al
2o
3, the sample that takes a morsel characterizes.
Comparative example 5
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 2g Al
2o
3bead, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAl-LDHs-Al
2o
3.
Step B: take 2g ZnAl-LDHs-Al
2o
3(in steps A, making), incipient impregnation SnCl
4the aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation H
2[PtCl
6] aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain PtSn/ZnAl-LDHs/Al
2o
3.
Step C: by the PtSn/ZnAl-LDHs-Al obtaining
2o
3in Muffle furnace, 750 DEG C of insulation 300min, are down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain PtSn/ZnAl-MMO/Al
2o
3, the sample that takes a morsel characterizes.
Embodiment 6
Get Pt/ZnAlSn-MMO/Al prepared by embodiment 5
2o
3the PtSn/ZnAl-MMO/Al preparing with comparative example 5
2o
3carry out hydroxide titration method and measure the relatively decentralization of metal active center platinum, the results are shown in following table:
Embodiment 7
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 2g Al
2o
3bead, 0.001mol SnCl
46H
2o, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, and 90 DEG C are stirred crystallization 12h, and product filtration washing is 7 to pH, and in 55 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAlSn-LDHs/Al
2o
3.
Step B: take 2g ZnAlSn-LDHs-Al
2o
3(in steps A, making), incipient impregnation Pd (NH
3)
4cl
2the aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain Pd/ZnAlSn-LDHs/Al
2o
3.
Step C: by the Pd/ZnAlSn-LDHs-Al obtaining
2o
3in Muffle furnace, 750 DEG C of insulation 300min, are down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain Pd/ZnAlSn-MMO/Al
2o
3, the sample that takes a morsel characterizes.
Comparative example 7
Steps A: by 0.01mol Zn (NO
3)
26H
2o, 2g Al
2o
3bead, 0.2mol urea are dissolved in 200ml deionized water prepares mixed solution, 90 DEG C of crystallization 12h, and product filtration washing is 7 to pH, in 100 DEG C of oven drying 10h, the sample that takes a morsel characterizes, and obtains ZnAl-LDHs-Al
2o
3.
Step B: take 2g ZnAl-LDHs-Al
2o
3(in steps A, making), incipient impregnation SnCl
4the aqueous solution, after 100 DEG C of oven drying 10h, incipient impregnation Pd (NH
3)
4cl
2the aqueous solution, evenly, physical absorption ion is removed in washing in concussion, and 80 DEG C of dry 12h, obtain PdSn/ZnAl-LDHs/Al
2o
3.
Step C: by the PdSn/ZnAl-LDHs-Al obtaining
2o
3in Muffle furnace, 750 DEG C of insulation 300min, are down to after room temperature H in tube furnace
2reduction, 750 DEG C of reduction 300min, obtain PdSn/ZnAl-MMO/Al
2o
3, the sample that takes a morsel characterizes.
Embodiment 8
Get Pd/ZnAlSn-MMO/Al prepared by embodiment 7
2o
3the PdSn/ZnAl-MMO/Al preparing with comparative example 7
2o
3carry out hydroxide titration method and measure the relatively decentralization of metal active center platinum, the results are shown in following table:
Claims (9)
1. a method that makes used additives control catalyst metals centre-height disperse, is characterized in that, comprises the following steps:
A. prepare hydrotalcite precursor [M
2+ 1-am
n+ a(OH)
2]
x+[A
y-] mH
2o, wherein, M
2+divalent metal, M
n+be high valent cationic, select Al
3+with a kind of promoter metal cation, the cationic molar percentage of promoter metal is controlled in 10%, A
y-it is the anion that enters interlayer; 0.1≤m≤0.8; 0.2≤a≤0.33;
B. the soluble compound of precious metal element is deposited on hydrotalcite precursor by conventional method, such as by platinum salt or containing the aqueous solution of platinum compounds or organic solution incipient impregnation to the hydrotalcite precursor making in step a, washing, dry;
C. the catalyst precarsor making in b is incubated to 1-5h high-temperature roasting at tube furnace 400-850 DEG C, then uses H
2reduce, can obtain the loaded catalyst of metal center high degree of dispersion.
2. according to the method for claim 1, it is characterized in that M
2+be preferably Zn
2+, Mg
2+, Ni
2+, Mn
2+in one.
3. according to the method for claim 1, it is characterized in that, promoter metal cation is that Tricationic or quadrivalent cation can replace former Tricationic Al
3+enter the metal cation of hydrotalcite laminate.
4. according to the method for claim 1, it is characterized in that, promoter metal cation is In
3+, Fe
3+, Cr
3+, Sn
4+, Zr
4+, Ti
4+, Ce
4+, Cr
3+one or more.
5. according to the method for claim 1, it is characterized in that, the hydrotalcite precursor growth in situ of step a is at Al
2o
3, SiO
2or TiO
2on bead, form multilevel hierarchy.
6. according to the method for claim 1, it is characterized in that, precious metal element is platinum, palladium, gold, rhodium, ruthenium or iridium.
7. according to the method for claim 1, it is characterized in that step b: by platinum salt or containing the aqueous solution of platinum compounds or organic solution incipient impregnation to the hydrotalcite precursor making in a, washing, dry, platinum load capacity is 0.2wt%-3wt%.
8. according to the method for claim 7, it is characterized in that platinum salt or have chloroplatinic acid, sodium chloroplatinate, ammoniation, ammonium chloroplatinate, dihydroxy platinous chloride or six hydroxyl platinic acid containing platinum compounds.
9. the catalyst preparing according to the either method of claim 1-8.
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